JP2005314171A - Hydrogen production apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hydrogen production apparatus for generating a gas containing hydrogen from a fuel, which can supply a satisfactory reformed gas even in a low temperature range of ≤500°C immediately after starting. <P>SOLUTION: The hydrogen production apparatus for generating a gas containing hydrogen from the fuel has an ozone generator at the front part of a reformer and is characterized by introducing air or water into the ozone generator, dissolving ozone generated in the ozone generator into water and/or the fuel between the ozone generator and the reformer, and introducing the resulting ozone-containing liquid into the fuel reformer. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

The present invention relates to a hydrogen production apparatus (also simply referred to as an H ₂ production apparatus) including a fuel reformer that generates a gas containing hydrogen from a hydrocarbon-based fuel.

  Solid polymer fuel cells are expected to be used as power sources for automobiles and the like because a high current density can be obtained even at a relatively low temperature. As a supply source of the hydrogen-containing gas to the solid polymer fuel cell, a fuel reformer capable of taking out the hydrogen-containing gas from the hydrocarbon fuel has been proposed.

In general, in a fuel reformer that takes out H ₂ from a fuel using only a reforming catalyst, H ₂ is taken out by two types of reactions, SR reaction and ATR reaction.

  Taking isooctane as an example, the ATR reaction is a reaction of fuel, air, and water, and is represented by the following reaction formula (1).

  On the other hand, the SR reaction is a fuel / water reaction and is represented by the following reaction formula (2).

Both reactions have advantages and disadvantages. Since the SR reaction is a reaction of only fuel and H ₂ O, a high H ₂ yield can be expected, but since it is an endothermic reaction, the reaction does not proceed unless heat is supplied. For this reason, the heater and the heat exchanger become very large, or a high temperature is required to sufficiently advance the reforming reaction, and the thermal energy increases. Therefore, it is difficult to make the reformer compact. On the other hand, in the case of the ATR reaction, oxygen and fuel in the air undergo a partial oxidation reaction, so heat is generated, and not only the reformer is made compact but also the startability is improved. However, since a part of the fuel is reacted with O ₂ , the amount of H ₂ obtained is reduced as compared with the SR reaction, or the H ₂ concentration obtained is decreased because it is diluted with N _{2 in} the air. there were.

  In addition, the reforming catalyst applied to such a reforming reaction is generally a pellet-shaped catalyst, which has a large pressure loss and causes problems such as pulverization due to contact with catalyst particles. On the other hand, a honeycomb-shaped catalyst in which a catalyst base is coated on a ceramic base material such as cordierite has also been proposed, but due to the characteristics of the ceramic base material, moldability is difficult and it is easy to fix in the reactor. In addition, since the wall thickness of the base material is thick, there is a limit to coat a large amount of the catalyst component.

  As a means for solving such a problem, Ti, Al, Si, Zr, Ni, Fe, Co, Cu, Zn, Pt, Pd, Ru, A material obtained by coating a metal honeycomb carrier with at least one catalyst selected from Rh has been proposed (see, for example, Patent Document 1).

In the catalyst described in Patent Document 1, since a catalyst having good heat transfer and good base material formability can be provided even in a reforming reaction with endotherm or heat generation, the temperature of the gas at the time of startup The hydrocarbon can be reformed immediately after startup.
JP 2000-126595 A (page 5, FIG. 5)

However, even if a hydrocarbon-based fuel is reacted using a conventional fuel reformer (H ₂ production apparatus) using the catalyst described in Patent Document 1, FIG. 5 on page 5 of Patent Document 1 is used. As is apparent, the reforming performance deteriorates at a low temperature range of 500 ° C. or lower, and there is a problem that sufficient reformed gas cannot be obtained at the time of startup.

In particular, solid polymer fuel cells, which are expected to be used as power sources for mobile vehicles such as fuel cell vehicles, aim to achieve performance equivalent to that of ordinary gasoline engine vehicles, such as fuel cell vehicle start-up performance (for example, standby time from start to start) ) Research and development is underway. In order to supply a large current for driving the motor required for starting this fuel cell vehicle, it is not possible to supply an electrode from the outside. Therefore, in addition to the output from an auxiliary power source such as a secondary battery or a capacitor, It is necessary to increase the amount of power generation (fuel cell output). However, in an automobile with a limited mounting space, it is difficult to increase the capacity of the auxiliary power source, and the amount of power that can be covered by the auxiliary power source is short. Therefore, it is desired to obtain a sufficient amount of power generated by the fuel cell from the earliest possible time, which can contribute to the reduction in size and weight of the auxiliary power supply. Therefore, in order to obtain a sufficient amount of power generated by the fuel cell, as a H ₂ production apparatus used as a hydrogen-containing gas supply source to the fuel cell, a sufficient amount of modification is possible even in a low temperature region of 500 ° C. or less immediately after startup. The thing which can supply quality gas is anxious.

Therefore, the present invention has been focused on the above-mentioned problems of the prior art, and a high H ₂ yield is obtained in a high temperature range (steady time) in an H ₂ production apparatus that generates a gas containing hydrogen from fuel. An object of the present invention is to provide an H ₂ production apparatus that improves the reforming performance in a low temperature range (500 ° C. or lower) while maintaining the merit of the usual SR reaction.

More specifically, in an H ₂ production apparatus that generates a gas containing hydrogen from fuel, a high H ₂ yield can be obtained in a high temperature range (steady state) by introducing fuel and water into the fuel reformer. While maintaining the merits of the usual SR reaction, the reforming performance in the low temperature range (500 ° C or lower), in particular, sufficient reformed gas can be supplied even in the low temperature range of 500 ° C or lower immediately after startup. An object of the present invention is to provide an H ₂ manufacturing apparatus with improved quality performance.

The present invention relates to an H ₂ production apparatus that generates a gas containing hydrogen from a fuel.
An ozone (simply referred to as O ₃ ) generator at the front of the fuel reformer, introducing air or water into the O ₃ generator;
Characterized in that the O ₃ which is generated in the O ₃ generator, dissolved in H _{2 O} and / or fuel between the O ₃ generator and fuel reformer, is introduced to the fuel reformer it can be achieved with H ₂ production apparatus according to.

With H ₂ production apparatus of the present invention generates a O ₃ by placing the O ₃ generator in front of the fuel reformer, the O ₃ between the O ₃ generator and fuel reformer H ₂ O and / or one dissolved in fuel is introduced into the fuel reformer together with other reforming raw materials (fuel or water), so that the reforming reaction is carried out by the reactivity with the fuel higher than O _2. It can be promoted, fuel to be reformed increases, and reformed gas increases. Further, a gas of O ₃ was heated O ₃ containing solution dissolved in H _{2 O} and fuel, mutually intermingled facilitates the other reforming raw material gas becomes fuel reacted with O ₃ is liable to react with water The reforming reaction is promoted compared to the normal SR reaction. Since such O ₃ generation can be performed at normal temperature (outside temperature) immediately after startup, it is not necessary to wait for the fuel reformer to warm up to a high temperature range exceeding 500 ° C. As a result, the reforming performance can be improved even in a low temperature range of 500 ° C. or less immediately after startup, and an H ₂ production apparatus capable of supplying a sufficient amount of reformed gas can be provided.

H ₂ production apparatus of the present invention, the H ₂ production apparatus for generating a gas containing hydrogen from the fuel, includes an O ₃ generator to the front of the reformer, introducing air or water to the O ₃ generator which is, the O ₃ generated in the O ₃ generator, dissolved in H _{2 O} and / or fuel between the O ₃ generator and the reformer, characterized in that introduced into the reformer It is. In the H ₂ production apparatus of the present invention, by having the above-described configuration, O ₃ is generated from air or water, dissolved in fuel or water, and introduced into the reformer. The reforming performance can be improved in a low temperature range of 500 ° C. or lower while maintaining.

Hereinafter, representative embodiments of the H ₂ manufacturing apparatus configured to have the above functions will be described in detail with reference to specific examples, comparative examples, and drawings.

First Embodiment (Example 1)
In Example 1, a first embodiment of the H ₂ production apparatus for generating a gas containing hydrogen from the fuel, provided with a discharge type of O ₃ generator to the front of the reformer, the O ₃ generates an air was introduced into the vessel, the O ₃ generated in the O ₃ generator, dissolved in H _{2 O} at between the O ₃ generator and the reformer, characterized in that introduced into the reformer H ₂ A specific embodiment of the manufacturing apparatus will be described.

FIG. 1 schematically shows an outline of a first embodiment of a fuel cell system incorporating the H ₂ production apparatus of the present invention.

As shown in FIG. 1, in the present embodiment, a discharge type O ₃ generator 13 is installed in the front stage of the fuel reformer 11, and air (denoted as Air in the figure) is supplied to the O ₃ generator 13. Introduce. By generating O ₃ from the air by the H ₂ production apparatus of this example, the ozone-reacted fuel easily reacts with water, and the reforming performance is improved as compared with the normal SR reaction shown in Comparative Example 1 described later. Can be promoted. As a result, the reforming performance can be improved in a low temperature range (500 ° C. or lower).

O _{2 in} the air is partially converted to O ₃ by the reaction of 3O ₂ → 2O ₃ by the discharge type O ₃ generator 13. The O ₃ concentration is about 3%, and when the amount of air supplied to the discharge-type O ₃ generator 13 is 0.78 m ³ N / h, the amount of O ₃ generated is about 30 kg / h. In addition, the power consumption in the discharge-type O ₃ generator 13 at that time requires about 30 kW to generate 1 kg / h of O ₃ .

When it is difficult to supply from an external power source as in a fuel cell vehicle, such power is supplied from a secondary battery or capacitor, which is an auxiliary power source, at startup, and then generated by the fuel cell. Supplied from Therefore, even in the case of a fuel cell vehicle, stable supply of O ₃ is possible immediately after startup.

Here, the O ₃ generator mainly includes a discharge type, an electrolysis type, and an ultraviolet lamp type (in the present invention, included in the discharge type).

The O ₃ generator that can be used in the present embodiment may be any generator that can partially convert O ₂ in the air to O ₃ by a reaction of 3O ₂ → 2O _3. The production cost of No. ₃ is the cheapest and can be suitably used. As the discharge type, those using a silent discharge method and a creeping discharge method mainly from the principle of discharge can be used.

In such a discharge-type O ₃ generator, a voltage of several k to 10,000 volts is applied to the air as a voltage to generate electrons due to the discharge, and the electrons dissociate O ₂ to generate O atoms. Thereby, a part of oxygen in the air can be changed to O ₃ . The reaction formula is as follows.

That is, O ₃ (specifically, O ₃ + O ₂ mixed gas) can be obtained as described above by electrically discharging air in the discharge-type O ₃ generator 13.

The air introduced into the discharge type O ₃ generator 13 is preferably dry air. Therefore, a dehumidifier (not shown) may be further installed in front of the discharge type O ₃ generator 13. Thereby, it is advantageous in that the O ₃ concentration can be improved by removing moisture contained in the air and sending dry air to the discharge-type O ₃ generator 13. In addition, it is possible to prevent OH radicals decomposed from moisture in the air from generating nitric acid from nitrogen oxides and deteriorating the electrodes of the discharge-type O ₃ generator 13, reducing the frequency of repair and replacement of parts. This is also advantageous.

Then, a part of the _{O 3} generated in the discharge type of _{O 3} generator 13, the water (in the figure with the _{O 3} generator 13 and the reformer _11, referred to as H 2 O (l). Parentheses 1 represents a liquid.) Ozone water (also referred to as O ₃ -containing water) is obtained by dissolving in 1). Specifically, as shown in FIG. 1, a gas containing _{O 3} generated in the _{O 3} generator 13 (hereinafter, also referred to as _{O 3} containing gas. _Mainly, O _3, O 2, _{N 2} gas) to the, Water is sprayed (sprayed), for example, in the form of a mist on the piping path between the O ₃ generator 13 and the reformer 11 to bring it into gas-liquid (cocurrent or countercurrent) contact, and O ₃ Is dissolved in water. In such a method, the amount of water sprayed (sprayed) can be adjusted according to the flow rate of the O ₃ -containing gas passing through the piping path, so that the concentration of O ₃ dissolved in water can be kept substantially constant. However, in the present invention, it is not limited to the above method, and various conventionally known dissolution methods may be applied, such as melting by bubbling O ₃ -containing gas into a water tank. .

Then, for example, it may be provided such as gas-liquid separator 15, and the ozone water _{(O 3} containing water), _{O 3} containing gas after _{O 3} dissolution treatment _(mainly, is a O 2, _{N 2} gas, non Containing dissolved O ₃ gas). The O ₃ -containing gas after the O ₃ dissolution treatment is exhausted out of the system, and then a reforming system that removes O ₃ with a catalyst. The reason for this is that not only O ₃ but also oxygen and nitrogen exist in the O ₃ -containing gas after the O ₃ dissolution treatment. Therefore, when introducing these gas components into the reformer 11, H ₂ is diluted and the H ₂ yield is lowered. For this purpose, the gas component is exhausted. The catalyst is not particularly limited as long as it can decompose O ₃ and can be a conventionally known catalyst. Specifically, Pt, Pd, and Rh are used as noble metals, Mn, Co, Cu, Fe, Ni, and Ag are used as additives, and γ-Al ₂ O ₃ , SiO ₂ , and TiO ₂ are used as substrates. It has been. The reason why O ₃ is removed is to prevent environmental pollution (air pollution) due to O ₃ .

On the other hand, the ozone water is heated by a heater or the like while being introduced into the reforming catalyst in the reformer 11, and becomes H ₂ O (g) + O ₃ (g). In front of the reformer 11, a fuel gas (indicated as fuel (g) in the figure. “G” in parentheses represents gas) is sent, and the reforming catalyst in the reformer 11 is fuel, H ₂ O, O ₃ is reacted. Most of the reaction is an SR reaction, but O ₃ assists the reaction. As a result, a gas containing hydrogen can be generated from a fuel such as methanol, methane, and gasoline with a high H ₂ yield.

The role of O ₃ here is considered to be as follows.

Since O ₃ is more reactive than O _2, it breaks some of the C—C bonds of the fuel to make it more easily reformed. Alternatively, it is effective to be more easily modified by being mixed with O ₃ and reacting to become an oxygen-containing compound. Therefore, it becomes easy to react with water and the fuel to be reformed increases.

  It is thought that the reforming performance is improved as described above. Here, the reforming performance specifically represents the following.

Improvement of fuel conversion rate, improvement of conversion rate at low temperature (500 ° C. or less), improvement of H ₂ selectivity, reduction of CO and CH ₄ . Regarding the improvement of the fuel conversion rate and the improvement of the low temperature conversion rate of 500 ° C. or less, the reaction of O ₃ is more reactive than O _2, and the effect that the fuel becomes easier to react, and O ₃ is mixed and reacted. By becoming like an oxygen-containing compound, there exists an effect that it becomes easier to modify | reform. In general, it is known that hydrocarbons having no oxygen such as isooctane are less reactive than compounds such as ethanol and methanol. In addition, the improvement of H ₂ selectivity and the reduction of CO and CH ₄ are also characteristic for oxygen-containing compounds. Generally, oxygen-containing compounds such as methanol use a catalyst such as Cu or Pd / ZnO. Then, it is known that CO and CH ₄ are reduced and H ₂ selectivity is improved. Therefore, it is considered that CO 3 and CH ₄ are reduced and H ₂ selectivity is improved by reacting O ₃ with the fuel to obtain a fuel such as an oxygen-containing compound.

Here, the fuel that can be used in the present invention is not particularly limited as long as it is a hydrocarbon-based fuel. For example, paraffins with hydrocarbons such as CH ₄ , C ₂ H ₆ , C ₃ H ₈ ; aromatics such as benzene and toluene; olefins such as C ₂ H ₄ , C ₃ H ₆ ; nafurans; , A mixture of kerosene, light oil or the like, or an alcohol such as methanol or ethanol.

In this embodiment, H ₂ O (g) + O ₃ (g) and fuel gas are adjusted and mixed between the fuel reformer 11 and the O ₃ generator 13 so as to obtain an appropriate blending ratio. . If the H ₂ O (g) + O ₃ (g) and the fuel are not mixed in advance, the effect as the reforming reaction is reduced. Therefore, it is desirable not to introduce the fuel reformer 11 directly but to mix it between the fuel reformer 11 and the O ₃ generator 13.

As the fuel reformer 11, for example, a fuel reformer having a reforming catalyst used for a normal SR reaction can be used as in Comparative Example 1 to be described later, but in part, O ₃ is used as an oxygen source. Therefore, a fuel reformer having a reforming catalyst used for the ATR reaction may be used.

The reforming catalyst used in the fuel reformer 11 is not particularly limited, and many reforming catalysts similar to those used in conventional fuel reformers are used for each type of fuel. It can be applied as it is. For example, when the reforming reaction is carried out using methane as a fuel, a catalyst such as Cu or Pd / ZnO that can reduce CO and CH ₄ and improve H ₂ selectivity as described above, Selected from Ti, Al, Si, Zr, Ni, Fe, Co, Cu, Zn, Pt, Pd, Ru, and Rh, which are hydrocarbon reforming catalysts having excellent thermal responsiveness described in Japanese Patent Publication (Patent Document 1) A material formed by coating at least one catalyst on a metal honeycomb carrier, Ru, Rh, Ir, Ni described in JP-A No. 2002-126522, etc. is impregnated in an Al ₂ O ₃ or ZrO ₂ carrier, and heat resistant oxidation such as a hydrocarbon reforming catalyst, such as those using ZrO 2, _MgO in the cocatalyst component comprising from the object, is also still can be used as a combination thereof as appropriate, are those in any limitation Not. That is, in the present invention, the catalyst used in the fuel reformer is matched with the O ₃ -containing raw material of the present invention (fuel + water + O ₃ , and there is also an embodiment containing O ₂ as shown in Example 4 described later). This is advantageous in that it does not require new development. Preferably, it is desirable to appropriately select and use a catalyst type having a higher reforming effect by O ₃ . However, in the present invention, as a catalyst type having a higher O ₃ reforming effect, it was obtained by improving the combination of existing catalyst types, combining, changing the design of the blending ratio, etc., or developing a completely new catalyst type. It goes without saying that things may be used.

Similarly, with respect to the reaction temperature and the space velocity, can be mainly applied conditions taking place in conventional fuel reformer by SR reaction, more O ₃ as modification effect becomes high, by appropriately adjusting Also good. That is, the reaction temperature in the fuel reformer 11 mainly due to the SR reaction may be adjusted in the same manner as in the past according to the fuel, the catalyst type, and the like. In general, the apparatus is operated from a low temperature range and then controlled to stabilize at a high temperature range of 500 to 800 ° C. in a steady state, but in the present invention, as described above, it is good even at a low temperature range of 500 ° C. or less. Therefore, it can be said that it may be operated in a lower temperature range than before. Also, the space velocity may be adjusted in the same manner as before, and GHSV (Gas Hourly Space Velocity) = exhaust gas amount (m ³ N / h) / catalyst amount (m ³ ) = 1000 to 300,000 (1 / H), and it is desirable to control within this range. However, at the time of start-up, etc., it is not limited to the above range, and it may be controlled so that it can quickly shift to a steady state, etc. Control according to the operating status of the device (start-up, steady-state, stop, etc.) To do. In addition, the reformer and ozone generator (further, dehumidifiers, shift reactors, prox reactors, fuel cells, etc. described later), in addition to temperature and space velocity, humidity, gas composition (gas concentration), gas In addition to heaters and pumps so that the flow rate (flow velocity), pressure, etc. can be controlled, these control devices, for example, temperature, humidity, pressure, flow rate, gas sensor detection units (measurement units), arithmetic processing units (adjustment) Part), an operation part such as a nozzle or a valve may be provided.

In the H ₂ manufacturing apparatus of the present embodiment, any apparatus having the fuel reformer 11 and the discharge-type O ₃ generator 13 may be used. That is, with H ₂ producing apparatus of this embodiment, O ₃ generator 13 in front of the fuel reformer 11 is provided, has a device structure capable of introducing air into the O ₃ generator 13. Further, between the fuel reformer 11 and the O ₃ generator 13, O ₃ generated by the O ₃ generator 13 is dissolved in H ₂ O, and the obtained ozone water is heated and vaporized. It has an apparatus configuration that can be introduced and supplied to the fuel reformer 11. Further, as long as it has a device structure capable of exhausting the O ₃ containing gas after O ₃ dissolution treatment outside the system.

In this embodiment, the outline of the fuel cell system in which the H ₂ manufacturing apparatus is incorporated is shown in a simplified manner. However, the H ₂ manufacturing apparatus of the present invention is limited to application to these fuel cell systems. It is not something. In the fuel cell system of the present embodiment, a shift reactor 17, a prox reactor 19, and a fuel cell 21 are provided at the rear of the fuel reformer 11 of the H ₂ production apparatus. Moreover, it has an apparatus configuration capable of introducing H ₂ O (g) between the fuel reformer 11 and the shift reactor 17, and between the shift reactor 17 and the prox reactor 19, between the prox reactor 19 and the fuel. It has an apparatus configuration capable of introducing air (oxygen-containing gas) between the batteries 21.

In the fuel cell system shown in the present embodiment, after generating a gas containing hydrogen from the fuel by the H ₂ production apparatus, the gas containing hydrogen from H ₂ production apparatus, H 2 _O introduced _(g) Then, the gas is sent to the shift reactor 15 to perform a shift reaction (CO + H ₂ O → CO ₂ + H ₂ ) to reduce the CO concentration in the hydrogen-containing gas and simultaneously generate hydrogen.

In the fuel cell system incorporating the above-described H ₂ production apparatus of the present invention, the gas composition containing hydrogen coming out of the H ₂ production apparatus differs in concentration due to the improvement of the reforming performance by ozone, but the gas type is It is not different from the conventional fuel reformer. Therefore, the apparatus configuration (catalyst type, catalyst shape, etc.), reaction temperature, space velocity, etc. of the shift reactor 17 and the prox reactor 19 provided in the rear part can be sufficiently applied without any particular change or improvement. Have advantages.

Moreover, carbon monoxide (CO) is produced | generated as a by-product by performing reforming reaction even if it uses any hydrocarbon fuel. That is, when a gas containing hydrogen is produced by reforming reaction (mainly SR reaction) of methanol, methane, gasoline, etc. of fuel with a conventional fuel reformer, about 1 to 25% as a by-product is produced. CO is generated. However, in this embodiment, since the CO concentration can be reduced by improving the reforming performance, the load on the rear shift reactor 17 and the prox reactor 19 may be light. Therefore, the catalyst life can be improved, and the frequency of maintenance (replacement period) can be reduced, which is advantageous in that the ripple effect on the fuel cell system can be obtained by incorporating the H ₂ production apparatus of the present invention. is there.

  Next, air (oxygen-containing gas) is introduced into the hydrogen-containing gas with reduced CO concentration from the shift reactor 17 and sent to the prox (selective oxidation removal of CO) reactor 19 to cover the Pt catalyst electrode of the fuel cell. A selective oxidation removal reaction of poisoning CO is performed, and the CO concentration is reduced to 100 ppm or less, preferably 10 ppm or less, which is a level usable for a fuel cell. The high-purity hydrogen-containing gas and air (oxygen-containing gas) thus obtained are supplied to the fuel electrode and the air electrode of the fuel cell 21, respectively.

(Comparative Example 1)
In Comparative Example 1, a comparative embodiment using a fuel reformer using a normal SR reaction will be described as an example of a conventional representative H ₂ production apparatus.

  FIG. 8 schematically shows an outline of a fuel cell system using a fuel reformer utilizing a normal SR reaction.

In FIG. 8, a fuel reformer 11 is used as the H ₂ production apparatus, and a shift reactor 17, a prox reactor 19, and a fuel cell 21 are provided in the rear part thereof. The fuel reformer 11 has an apparatus configuration capable of directly introducing fuel and water. Furthermore, it has an apparatus configuration in which H ₂ O (g) can be introduced between the fuel reformer 11 and the shift reactor 17, and between the shift reactor 17 and the prox reactor 19, the prox reactor 19 and the fuel. It has an apparatus configuration capable of introducing air (oxygen-containing gas) between the batteries 21.

In the fuel cell system using the fuel reformer 11 shown in this comparative example, the SR reaction shown in the above reaction formula (2) is performed by introducing fuel and water into the H ₂ production apparatus, and hydrogen is contained from the fuel. To generate gas. In the fuel cell system of the present comparative example, as described above, as the gas composition containing hydrogen coming out of the fuel reformer 11, for example, methanol, methane, gasoline, or the like of fuel is used as an existing fuel reformer. Even if a gas containing hydrogen is produced by SR reaction at, the reforming performance improvement effect by ozone is not obtained, so the reforming effect in the low temperature (500 ° C. or lower) region is not sufficient, and the high temperature A sufficient reforming effect (high H ₂ yield) can be obtained by carrying out the reaction in the region, but about 1 to 25% of CO is produced as a by-product as usual. Therefore, H ₂ O (g) is introduced into the hydrogen-containing gas from the fuel reformer 11 and sent to the shift reactor 17 to perform a shift reaction (CO + H ₂ O → CO ₂ + H ₂ ). Reduces the CO concentration of hydrogen and at the same time produces hydrogen. Further, air (oxygen-containing gas) is introduced into the hydrogen-containing gas with reduced CO concentration from the shift reactor 17 and sent to the prox (CO selective oxidation removal) reactor 19 to cover the Pt catalyst electrode of the fuel cell 21. The selective oxidation removal reaction of poisoning CO is performed, and the CO concentration is reduced to about 10 to 100 ppm, which is a level usable for the fuel cell 21. The high-purity hydrogen-containing gas and air (oxygen-containing gas) thus obtained are supplied to the fuel electrode and the air electrode of the fuel cell 21, respectively.

In this comparative example, unlike the first embodiment, the reforming performance improvement effect by ozone immediately after startup cannot be obtained. Therefore, sufficient reformed gas cannot be generated by the fuel reformer 11 in a low temperature range of 500 ° C. or less immediately after startup. As a result, the fuel cell 21 using the reformed gas (hydrogen gas) as a raw material cannot produce a large amount of power generation due to insufficient hydrogen supply. Therefore, the fuel cell 21 cannot sufficiently supply electric power for obtaining a motor driving force necessary for starting and accelerating the automobile. As a result, it was necessary to install a large-capacity auxiliary power source (secondary battery or capacitor) just to cover the shortage of power from the fuel cell immediately after startup, making it difficult to provide a wide interior space. . Alternatively, the car could not be started for ten or more seconds until the temperature reached a high temperature range exceeding 500 ° C. In this embodiment, it can be said that it is extremely useful in that it is not necessary to mount such a standby time and a large-capacity auxiliary power supply. Also, in this comparative example, unlike Example 1 above, O ₃ cannot react with the fuel to make a fuel such as an oxygen-containing compound, so that the CO, CH ₄ reduction effect and H ₂ selectivity can be reduced. Improvement effect is difficult to obtain.

Second Embodiment (Example 2)
In Example 2, as a second embodiment of the H ₂ production apparatus that generates hydrogen-containing gas from fuel, an ozone generator (discharge type) is provided at the front of the reformer, and air is supplied to the ozone generator. was introduced into the ozone generated by said ozone generator, dissolved in the fuel between the ozone generator and the reformer, concrete of H ₂ production apparatus characterized by introducing the reformer The embodiment will be described.

In Example 2, the device configuration is almost same with H ₂ production apparatus of Example 1, differs from, O ₃ and O ₃ generated by the generator, the fuel liquid rather than liquid water (l) dissolved in, then the ozone fuel is that device configuration that can be added to H _{2 O} (g) gasified rather than fuel gas. Except for these points, the apparatus configuration is the same as that of the H ₂ manufacturing apparatus of the first embodiment. Therefore, in this embodiment, the description of the fuel cell system other than the H ₂ manufacturing apparatus, including the drawings, is omitted.

FIG. 2 schematically shows an outline of the second embodiment of the H ₂ production apparatus of the present invention.

As shown in FIG. 2, with H ₂ producing apparatus of this embodiment, by introducing air into the O ₃ generator 13 to generate O _3. This point is as described in the first embodiment.

Next, in this embodiment, a part of O ₃ generated by the discharge-type O ₃ generator 13 is fuel (fuel (l) in the figure) between the O ₃ generator 13 and the reformer 11. It becomes an ozone fuel (solution). Specifically, with respect to O ₃ containing gas generated in O ₃ generator 13, the fuel on the pipe path between the O ₃ generator 13 and the reformer 11, for example, a mist shape to be sprayed (spraying Etc.) to bring gas and liquid (cocurrent or countercurrent) into contact with each other to dissolve O ₃ in the fuel. In such a method, the fuel supply amount to be sprayed (sprayed) can be adjusted in accordance with the flow rate of the O ₃ -containing gas passing through the piping path, so that the concentration of O ₃ dissolved in the fuel can be kept substantially constant. However, the present invention is not limited to the above-described method, and various conventionally known dissolution methods may be applied, such as melting by blowing (bubbled) an O ₃ -containing gas into the fuel tank. is there.

Then, for example, may be provided such as gas-liquid separator 15 is separated into the ozone fuel, and O ₃ content gas after O ₃ dissolution process. The O ₃ -containing gas after the O ₃ dissolution treatment is exhausted out of the system. On the other hand, the ozone fuel is heated by a heater or the like while being introduced into the reforming catalyst in the reformer 11, and becomes Fuel (g) + O ₃ (g). In front of the reformer 11, water is fed as a gas component (denoted as H ₂ O (g) in the figure), and fuel, H ₂ O, and O ₃ are reacted with the reforming catalyst in the reformer 11. . Most of the reaction is an SR reaction, but O ₃ assists the reaction. As a result, a gas containing hydrogen can be generated from a fuel such as methanol, methane, and gasoline with a high H ₂ yield.

In particular, in Example 1, ozone was dissolved in water and the fuel was supplied as a gas component, but in Example 2, ozone was dissolved in the fuel and water was sent as a gas component. In general, the ozone solubility of fuel is higher than the ozone solubility of water. For example, isooctane has a partition coefficient D = 1.5 at 0 ° C., but the ozone solubility of water has a partition coefficient D = 0.49 at 0 ° C. This indicates that isooctane is about 3 times easier to dissolve ozone than water. Therefore, the amount of O ₃ introduced into the reforming catalyst of the reformer 11 is increased about three times compared to the first embodiment, and the reforming performance is also increased. In addition to this, the fuel is mixed with ozone in a liquid state, which is advantageous in that the reactivity between ozone and fuel is dramatically increased and the reforming performance is improved as compared with the first embodiment. . As a result, in this example, good reforming performance can be exhibited even in a low temperature range of 500 ° C. or lower.

Third Embodiment (Example 3)
In Example 3, as a third embodiment of the H ₂ production apparatus that generates hydrogen-containing gas from fuel, an ozone generator (discharge type) is provided at the front of the reformer, and air is supplied to the ozone generator. The H ₂ production apparatus is characterized in that the ozone generated in the ozone generator is dissolved in fuel and water between the ozone generator and the reformer and introduced into the reformer. A specific embodiment will be described.

In Example 3, devices on configuration is almost same with H ₂ producing apparatus of the first embodiment, is different from, rather than the O ₃ generated in the O ₃ generator only water, water and fuel (water and fuel In which the ozone water and the ozone fuel are introduced into the reformer without adding the fuel gas. Except for these points, the apparatus configuration is the same as that of the H ₂ manufacturing apparatus of the first embodiment. Therefore, in this embodiment, the description of the fuel cell system other than the H ₂ manufacturing apparatus, including the drawings, is omitted.

FIG. 3 schematically shows the outline of the third embodiment of the H ₂ production apparatus of the present invention.

As shown in FIG. 3, with H ₂ producing apparatus of this embodiment, by introducing air into the O ₃ generator 13 to generate O _3. This point is as described in the first embodiment.

Next, in the present embodiment, a part of O ₃ generated by the discharge-type O ₃ generator 13 is water (l) and fuel (l) between the O ₃ generator 13 and the reformer 11. By dissolving it in ozone water, it becomes ozone water and ozone fuel (solution). Specifically, with respect to O ₃ containing gas generated in O ₃ generator 13, the water and fuel on the pipe path between the O ₃ generator 13 and the reformer 11, for example, in the mist spray O ₃ is dissolved in water and fuel by contacting (spraying) the gas and liquid (cocurrent or countercurrent). In this method, the amount of water sprayed (sprayed) and the amount of fuel supplied can be adjusted in accordance with the flow rate of the O ₃ -containing gas passing through the piping path, so that the concentration of O ₃ dissolved in water and fuel can be made substantially constant. Can keep. Further, the mixing ratio of water and fuel at this time is preferably the same as the mixing ratio when introduced into the reformer 11. However, in the present invention, it is not limited to the above-mentioned method, and various conventionally known dissolution methods such as blowing (bubbled) an O ₃ containing gas into a tank containing water and fuel may be used. The law is applicable. Here, when water and fuel can be dissolved at an arbitrary ratio, fuel water in which water and fuel are mixed in advance may be prepared, and O ₃ may be dissolved therein. In addition, when water and fuel are hardly soluble or insoluble and are separated into two phases of an aqueous phase and a fuel phase, as shown in FIG. 3, O ₃ is dissolved separately in water and fuel. Also good. In this case, it is desirable to dissolve in water having high solubility of O ₃ , and then dissolve in water. However, it may be performed at the same time, or may be dissolved in water and fuel in order. It is not limited.

Then, for example, may be provided such as gas-liquid separator 15, and the ozone water and ozone fuel (which may be ozone fuel water), it separated into the O ₃ containing gas after O ₃ dissolution process. The O ₃ -containing gas after the O ₃ dissolution treatment is exhausted out of the system. On the other hand, ozone water and ozone fuel (which may be ozone fuel water) are heated by a heater or the like while being introduced into the reforming catalyst in the reformer 11, and H ₂ O (g) + Fuel (g) + O ₃ (g). These are sent to the reformer 11, and the fuel, H ₂ O, and O ₃ are reacted with the reforming catalyst in the reformer 11. Most of the reaction is an SR reaction, but O ₃ assists the reaction. As a result, a gas containing hydrogen can be generated from a fuel such as methanol, methane, and gasoline with a high H ₂ yield.

  In Examples 1 and 2, one of the fuel and water is introduced as a liquid and ozone is dissolved therein, while the other is introduced as a gas and sent to the reformer. However, as in the present embodiment, both fuel and water may be introduced in liquid form, and at least the reforming performance is increased as compared with Embodiment 1. This is because fuel is generally more soluble in ozone than water. Therefore, a solution in which fuel and water are mixed has higher ozone solubility than that of water alone. That is, ozone dissolved in the solution in which water and fuel are dissolved increases as compared with the first embodiment. Therefore, the amount of ozone that reacts with the fuel increases as compared with the first embodiment. Further, since the fuel comes into contact with ozone in a liquid (small volume) state, the reactivity between the fuel and ozone is increased, and the reforming reaction can be promoted as compared with the first embodiment. As a result, also in this example, good reforming performance can be expressed even in a low temperature range of 500 ° C. or lower.

Fourth Embodiment (Example 4)
In Example 4, a fourth embodiment of the H ₂ production apparatus for generating a gas containing hydrogen from the fuel, dissolved from the O ₃ containing gas coming out of the O ₃ generator O ₃ in water and / or fuel A specific embodiment of the H ₂ production apparatus characterized in that a part of the O ₃ -containing gas after being introduced into the reformer will be described.

That is, in Example 4, devices on configuration is almost same with H ₂ production apparatus of the third embodiment, differs from the O ₃ from O ₃ containing gas coming out of the O ₃ generator, water and fuel some of the O ₃ containing gas was dissolved in in that the device configured to be introduced into the reformer is provided. By having such an apparatus configuration, an appropriate amount of a part of ozone gas (including other gas components) that does not dissolve in fuel or water can be supplied to the reforming catalyst in the reformer, and the reforming performance can be improved. . Except for these points, the apparatus configuration is the same as that of the H ₂ manufacturing apparatus of the third embodiment. Therefore, in this embodiment, the description of the fuel cell system other than the H ₂ manufacturing apparatus, including the drawings, is omitted.

FIG. 4 schematically shows the outline of the third embodiment of the H ₂ production apparatus of the present invention.

As shown in FIG. 4, with H ₂ producing apparatus of this embodiment, by introducing air into the O ₃ generator 13 to generate O _3. This point is as described in the first embodiment.

Next, a part of O ₃ generated by the discharge-type O ₃ generator 13 is dissolved in water (l) and fuel (l) between the O ₃ generator 13 and the reformer 11. It becomes ozone water and ozone fuel (solution). Specifically, with respect to O ₃ containing gas generated in O ₃ generator 13, the water and fuel on the pipe path between the O ₃ generator 13 and the reformer 11, for example, in the mist spray O ₃ is dissolved in water and fuel by contacting (spraying) the gas and liquid (cocurrent or countercurrent). In this method, the amount of water sprayed (sprayed) and the amount of fuel supplied can be adjusted in accordance with the flow rate of the O ₃ -containing gas passing through the piping path, so that the concentration of O ₃ dissolved in water and fuel can be made substantially constant. Can keep. Further, the mixing ratio of water and fuel at this time is preferably the same as the mixing ratio when introduced into the reformer 11. However, in the present invention, it is not limited to the above-mentioned method, and various conventionally known dissolution methods such as blowing (bubbled) an O ₃ containing gas into a tank containing water and fuel may be used. The law is applicable. Here, when water and fuel can be dissolved at an arbitrary ratio, fuel water in which water and fuel are mixed in advance may be prepared, and O ₃ may be dissolved therein. In addition, when water and fuel are hardly soluble or insoluble and are separated into two phases of an aqueous phase and a fuel phase, as shown in FIG. 3, O ₃ is dissolved separately in water and fuel. Also good. In this case, it is desirable to dissolve in water having high solubility of O ₃ , and then dissolve in water. However, it may be performed at the same time, or may be dissolved in water and fuel in order. It is not limited.

Then, for example, may be provided such as gas-liquid separator 15, and the ozone water and ozone fuel (which may be ozone fuel water), it separated into the O ₃ containing gas after O ₃ dissolution process.

In this embodiment, O ₃ dissolution treatment O ₃ containing gas instead of the exhaust out of the total amount based the later was a part of O ₃ containing gas after O ₃ dissolving treatment to be introduced into the reformer 11 Is.

In Examples 1, 2, and 3, O ₃ that does not dissolve in the fuel and / or water is exhausted, and thereafter, the reforming system removes O ₃ with a catalyst. The reason for this is that not only O ₃ but also oxygen and nitrogen exist in the O ₃ -containing gas after the O ₃ dissolution treatment. Therefore, when introducing these gas components into the reformer 11, H ₂ is diluted and the H ₂ yield is lowered. For this reason, in the above Examples 1 to 3, the gas component was exhausted. However, by introducing some oxygen or ozone into the reformer 11, the reaction can be promoted and the reforming performance can be improved. The catalyst is not particularly limited as long as it can decompose O ₃ and can be a conventionally known catalyst. Specifically, Pt, Pd, and Rh are used as noble metals, Mn, Co, Cu, Fe, Ni, and Ag are used as additives, and γ-Al ₂ O ₃ , SiO ₂ , and TiO ₂ are used as substrates. It has been. The reason why O ₃ is removed is to prevent environmental pollution (air pollution) due to O ₃ . However, in this example, by introducing some oxygen or ozone into the reformer, the reaction can be promoted and the reforming performance can be improved. That is, it is better than Examples 1, 2, and 3 if an appropriate amount is introduced into the reformer 11 so that the effect of improving the reforming performance is greater than the dilution effect due to the gas component. The reforming performance can be obtained. Here, since some oxygen and ozone are necessary, only a necessary amount of oxygen or ozone is introduced into the reformer 11 using such a partial oxygen or ozone permeable membrane or separation membrane. May be. By doing so, dilution of H ₂ by N ₂ gas occupying most of the O ₃ -containing gas after the O ₃ dissolution treatment can be further reduced. Incidentally, O ₃ containing gas after O ₃ dissolution process which is not introduced into the reformer is discharged in the same manner as in Example 1-3. As a result, in this embodiment, the reforming performance in the reformer can be further improved, and the reforming performance can be improved in a low temperature range (500 ° C. or lower).

On the other hand, ozone water and ozone fuel (which may be ozone fuel water) are heated by a heater or the like while being introduced into the reforming catalyst in the reformer 11 as in the third embodiment, and H ₂ O (G) + Fuel (g) + O ₃ (g). These are sent to the reformer 11, and the fuel, H ₂ O, and O ₃ are reacted with the reforming catalyst in the reformer 11. Most of the reaction is an SR reaction, but O ₃ assists the reaction. As a result, a gas containing hydrogen can be generated from a fuel such as methanol, methane, and gasoline with a high H ₂ yield.

  Also in the present embodiment, when both fuel and water are introduced as liquids as in the third embodiment, the reforming performance is increased as compared with the first embodiment. This is because fuel is generally more soluble in ozone than water. Therefore, a solution in which fuel and water are mixed has higher ozone solubility than that of water alone. That is, ozone dissolved in the solution in which water and fuel are dissolved increases as compared with the first embodiment. Therefore, the amount of ozone that reacts with the fuel increases as compared with the first embodiment. Further, since the fuel comes into contact with ozone in a liquid (small volume) state, the reactivity between the fuel and ozone is increased, and the reforming reaction can be promoted as compared with the first embodiment. As a result, also in this example, good reforming performance can be expressed even in a low temperature range of 500 ° C. or lower.

Fifth embodiment (Example 5)
In Example 5, as a fifth embodiment of the H ₂ production apparatus for generating a gas containing hydrogen from fuel, an O ₃ generator (electrolytic type) is provided at the front of the reformer, and water is supplied to the ozone. was introduced to the generator, the O ₃ generated in the O ₃ generator, dissolved in H _{2 O} at between the O ₃ generator and the reformer, characterized in that introduced into the reformer H ₂ A specific embodiment of the manufacturing apparatus will be described. Further in this embodiment, H ₂ production comprising provided with a device configuration in which O ₃ from O ₃ containing gas coming out of the O ₃ generator introducing O ₃ containing gas was dissolved in liquid water to the reformer An apparatus will be described as an example.

That is, the fifth embodiment uses an electrolytic O ₃ generator instead of the discharge O ₃ generator used in the first, second, _third , and fourth embodiments. Therefore, in the present embodiment, the fuel cell system (shift reactor, prox reactor, fuel cell, etc.) other than the H ₂ production apparatus is the same as that in the first embodiment, and the description thereof is omitted including the drawings. To do.

FIG. 5 schematically shows an outline of the fifth embodiment of the H ₂ production apparatus of the present invention.

As shown in FIG. 5, in the H ₂ production apparatus of this embodiment, an electrolysis type O ₃ generator 23 is installed in front of the fuel reformer 11. Along with this, the configuration in which introducing water into O ₃ generator 23, furthermore, O ₃ dissolution treatment after the O ₃ after the O ₃ containing gas obtained in O ₃ generator 23 is dissolved in water Except for the point that an apparatus configuration for introducing the contained gas into the reformer 11 without exhausting it out of the system is provided, the apparatus configuration is substantially the same as that described in the H ₂ manufacturing apparatus of the first embodiment. It is.

In the present embodiment, liquid water (for generating O ₃ ) is introduced into an electrolysis-type O ₃ generator 23 installed at the front stage of the fuel reformer 11. In electrolysis formula O ₃ generator 23 used in this embodiment, since immediately after the start introducing water (O ₃ for generating), it is possible to generate a high concentration of O _3, fuel and ozone reaction It becomes easy to react with water, and the reforming performance can be promoted as compared with the normal SR reaction. As a result, the reforming performance can be improved in a low temperature range of 500 ° C. or lower. In particular, the points described below are advantageous in that a higher reforming effect than in Examples 1 to 4 can be obtained.

Electrolytic O ₃ generator: When water is electrolyzed at a high density, H ₂ , O ₂ and O ₃ are generated. The reaction formula for O ₃ generation is 3H ₂ O → O ₃ + 3H ₂ . The O ₃ generation concentration is about 20 to 35% by volume. The generated amount is 0.1 to 1 kg / h when the water supply amount is 0.06 to 10 l / h. The power consumption is about 100 kW to generate 1 kg / h O ₃ .

That is, compared with the electrolysis type and discharge type O ₃ generators, there is the following difference in the power consumption required to generate 1 kg / h of O ₃ .

Discharge type: 1 kg / h × 3/100 (O ₃ concentration 3%) → 0.03 kW · kg / h (power 30 kW)
Electrolysis type: 1 kg / h × 20/100 (O ₃ concentration 20%) → 2 kW · kg / h (power 100 kW)
Thus, although the amount of electric power is about three times higher in the electrolytic method, O ₃ having a higher concentration (20%) is generated than in the discharge method. Just because in a high concentration O _3, solubility not significantly improved with respect to water. However, unlike Examples 1, 2, 3, and 4, since O ₃ is not generated from air, it is not necessary to consider dilution of H _{2 with} N ₂ . That is, there is no need to exhaust the gas. Moreover Of O ₃ or H ₂ generated in the O ₃ generator 23, with respect to H _2, O ₃ is not dissolved in water can be introduced directly into the reforming catalyst of the reformer 11. Therefore, even O ₃ which is not dissolved in water can be used, and the reactivity of the reforming catalyst can be further improved by the reaction with O ₃ . Therefore, the reforming performance is improved as compared with Examples 1, 2, 3, and 4.

The electrical resolving O ₃ water supplied to the generator 23 from the same water storage tank with water using a O _3-containing gas obtained in O ₃ generator 23 to cause dissolved, distributed a part May be supplied. Alternatively, another water storage tank may be provided and supplied from there. Furthermore, there is no particular limitation such that water generated by the reaction in the fuel cell may be recovered and supplied.

Then, part of the _{O 3} generated by the electrolysis formula _{O 3} generator 23, in water (FIG liquid between the _{O 3} generator 23 and the reformer _11, and H 2 O (l) It becomes ozone water by being dissolved in. The details are as described in the first embodiment.

Then, for example, may be provided such as gas-liquid separator 15, and the ozone water _{(O 3} containing water), _{O 3 O 3} containing gas after dissolution treatment (mainly, is a _{H 2} gas, undissolved _{O 3} Gas). Since the O ₃ -containing gas composition after the O ₃ dissolution treatment is H ₂ and O _3, they are introduced into the reforming catalyst in the reformer 11 without exhausting out of the system. On the other hand, the ozone water is heated by a heater or the like while being introduced into the reforming catalyst in the reformer 11, and becomes H ₂ O (g) + O ₃ (g). Fuel gas (referred to as fuel (g) in the figure) is sent before the reformer 11, and together with the O ₃ -containing gas after the previous O ₃ dissolution treatment, the reforming catalyst in the reformer 11 in the _fuel, H 2 O, the reaction of _{O 3 (H 2} in _{O 3} content in the gas after _{O 3} dissolution process is not used in the reaction). Most of the reaction is an SR reaction, but O ₃ assists the reaction. As a result, a gas containing hydrogen can be generated from a fuel such as methanol, methane, and gasoline with a high H ₂ yield.

In the present embodiment, unlike the first, _second , _third , and fourth embodiments, the electrolytic O ₃ generator 23 generates a considerable amount of H _2, so that it is introduced into the total reformer 11. Instead, some or all of H ₂ may be supplied directly to the fuel cell. In order to separate and recover H ₂ from the gas obtained by the electrolysis-type O ₃ generator 23, a conventionally known hydrogen separation technique can be appropriately used. For example, a hydrogen separation membrane can be used. This may be either before or after dissolving the O ₃ -containing gas in water.

Sixth Embodiment (Example 6)
In Example 6, as a sixth embodiment of the H ₂ production apparatus for generating a gas containing hydrogen from fuel, an ozone generator (electrolysis type) is provided at the front of the reformer, and water is generated by the ozone. A specific example of the H ₂ production apparatus, wherein the ozone generated in the ozone generator and dissolved in the fuel between the ozone generator and the reformer is introduced into the reformer and introduced into the reformer Various embodiments will be described. Furthermore, in this embodiment, H ₂ production is provided with an apparatus configuration for introducing O ₃ -containing gas after dissolving O ₃ into liquid fuel from O ₃ -containing gas coming out of the O ₃ generator to the reformer. An apparatus will be described as an example.

Example 6 is almost the same as the H ₂ production apparatus of Example 5 in terms of the apparatus configuration, except that the O ₃ -containing gas generated by the electrolytic O ₃ generator is not liquid water. It is dissolved in the liquid fuel (l), and then the ozone water is heated to gasify it. Instead of adding the gasified fuel to this, the ozone fuel is heated to gasify and gasified H ₂ O (G) is the point which the apparatus structure which can add is provided. Except for these points, the apparatus configuration is the same as that of the H ₂ manufacturing apparatus of the fifth embodiment. Therefore, in this embodiment, the description of the fuel cell system other than the H ₂ manufacturing apparatus, including the drawings, is omitted.

FIG. 6 schematically shows the outline of the sixth embodiment of the H ₂ production apparatus of the present invention.

As shown in FIG. 6, in the H ₂ production apparatus of this embodiment, water (liquid; mainly for O ₃ generation) is introduced into an electrolysis-type O ₃ generator 23, and an O ₃ -containing gas (mainly O _{3 is} generated). ₃ + H ₂ ). This point is as described in the fifth embodiment.

Then, in the present embodiment, a part of the O ₃ containing gas generated in O ₃ generator 23, by dissolving in the fuel in the liquid between the O ₃ generator 23 and the reformer 11, ozone fuel (Solution). The details are as described in the second embodiment.

Then, for example, may be provided such as gas-liquid separator 15 is separated into the ozone fuel, and O ₃ content gas after O ₃ dissolution process. Since the O ₃ -containing gas composition after the O ₃ dissolution treatment is H ₂ and O _3, they are introduced into the reforming catalyst in the reformer 11 without exhausting out of the system. On the other hand, the ozone fuel is heated by a heater or the like while being introduced into the reforming catalyst in the reformer 11, and becomes Fuel (g) + O ₃ (g). In front of the reformer 11, water is fed as a gas component (denoted as H ₂ O (g) in the figure) and is combined with the O ₃ -containing gas after the previous O ₃ dissolution treatment in the reformer 11. the fuel reforming _catalyst, H 2 O, the reaction of _{O 3 (O 3} dissolution treatment of _{H 2 O 3} content in the gas after is not reacted). Most of the reaction is an SR reaction, but O ₃ assists the reaction. As a result, a gas containing hydrogen can be generated from a fuel such as methanol, methane, and gasoline with a high H ₂ yield.

In Example 6, as described in Example 2, the solubility of O ₃ is higher in fuel than in water. Therefore, the amount of O ₃ consumed for the reaction is increased as compared with Example 5. Further, by dissolving O ₃ in the liquid fuel, the fuel comes into contact with O _{3 in a} liquid (small volume) state, and thus the reactivity between the fuel and O ₃ is dramatically increased. The reforming performance is further increased. Therefore, also in the present embodiment, the reforming improvement effect by O ₃ can be obtained from the time of start-up, so that the reforming performance can be improved in a low temperature range of 500 ° C. or lower.

Seventh embodiment (Example 7)
In Example 7, as a seventh embodiment of the H ₂ production apparatus for generating a gas containing hydrogen from fuel, an electrolytic O ₃ generator is provided at the front of the reformer, and water is supplied to the O _3. H ₃ is introduced into a generator, and O ₃ generated by the O ₃ generator is dissolved in fuel and water between the O ₃ generator and the reformer and introduced into the reformer. ₂ A specific embodiment of the manufacturing apparatus will be described. Further, in this embodiment, the apparatus has an apparatus configuration for introducing an O ₃ -containing gas obtained by dissolving O ₃ into liquid fuel and water from the O ₃ -containing gas that has come out of the O ₃ generator to the reformer. _{2 A} manufacturing apparatus will be described as an example.

In Example 7, the device configuration is almost same with H ₂ production apparatus of Example 5, is different, the O ₃ generated by the electrolysis formula O ₃ generator not only water, the water and fuel An apparatus configuration is provided in which ozone water and ozone fuel are introduced into the reformer without adding fuel gas after being dissolved in (including a mixed solution of water and fuel). Except for these points, the apparatus configuration is the same as that of the H ₂ manufacturing apparatus of the fifth embodiment. Therefore, in this embodiment, the description of the fuel cell system other than the H ₂ manufacturing apparatus, including the drawings, is omitted.

FIG. 7 schematically shows the outline of the seventh embodiment of the H ₂ production apparatus of the present invention.

As shown in FIG. 7, in the H ₂ production apparatus of this embodiment, water (liquid; mainly for O ₃ generation) is introduced into an electrolysis-type O ₃ generator 23, and an O ₃ -containing gas (mainly O ₃ generation). ₃ + H ₂ ). This point is as described in the fifth embodiment.

Then, in the present embodiment, a part of the O ₃ generated in the O ₃ generator 23, with the O ₃ generator 23 and the reformer 11, by dissolving in water and liquid fuels, ozone Water and ozone fuel (solution). The details are as described in the third embodiment.

Then, for example, may be provided such as gas-liquid separator 15, and the ozone water and ozone fuel (which may be ozone fuel water), it separated into the O ₃ containing gas after O ₃ dissolution process. Since the O ₃ -containing gas after the O ₃ dissolution treatment is H ₂ and O _3, it is introduced into the reforming catalyst in the reformer 11 without exhausting out of the system. On the other hand, ozone water and ozone fuel (which may be ozone fuel water) are heated by a heater or the like while being introduced into the reforming catalyst in the reformer 11, and H ₂ O (g) + Fuel (g) + O ₃ (g). These are fed into the reformer 11, and together with the O ₃ -containing gas after the previous O ₃ dissolution treatment, the fuel, H ₂ O, and O ₃ are reacted with the reforming catalyst in the reformer 11 (O ₃ dissolution) H ₂ in the O ₃ -containing gas after the treatment is not subjected to the reaction). Most of the reaction is an SR reaction, but O ₃ assists the reaction. As a result, a gas containing hydrogen can be generated from a fuel such as methanol, methane, and gasoline with a high H ₂ yield.

In Examples 5 and 6, one of the fuel and water is introduced as a liquid and O ₃ is dissolved therein, while the other is introduced as a gas and sent to the reformer. However, as in the present embodiment, both fuel and water may be introduced as liquids, and at least the reforming performance is increased as compared with the fifth embodiment. This is because fuel is generally more soluble in O ₃ than water. Therefore, a solution in which fuel and water are mixed has a higher solubility of O ₃ than water alone. That is, O ₃ dissolved in a solution in which water and fuel are dissolved is increased as compared with Example 5. Therefore, the amount of O ₃ that reacts with the fuel increases as compared with Example 5. Furthermore, since the fuel comes into contact with O _{3 in a} liquid (small volume) state, the reactivity between the fuel and O ₃ increases, and the reforming reaction can be promoted as compared with Example 5. As a result, also in this example, good reforming performance can be exhibited even in a low temperature range of 500 ° C. or lower.

The outline of the first embodiment of a fuel cell system incorporating of H ₂ production apparatus of the present invention is a schematic diagram schematically showing. The outline of the second embodiment of the H ₂ production apparatus of the present invention is a schematic diagram schematically showing. Description of the third embodiment of the H ₂ production apparatus of the present invention is a schematic diagram schematically showing. Description of the fourth embodiment of the H ₂ production apparatus of the present invention is a schematic diagram schematically showing. The outline of the fifth embodiment of the H ₂ production apparatus of the present invention is a schematic diagram schematically showing. An outline of a sixth embodiment of the H ₂ production apparatus of the present invention is a schematic diagram schematically showing. An outline of a seventh embodiment of the H ₂ production apparatus of the present invention is a schematic diagram schematically showing. It is the schematic which represented the outline | summary typically the fuel cell system using the fuel reformer using the conventional normal SR reaction.

Explanation of symbols

11 Fuel reformer (SR reaction reformer),
13 Discharge O ₃ generator,
15 Gas-liquid separation part,
17 shift reactor,
19 prox reactor,
21 Fuel cell,
23 Electrolytic O ₃ generator.

Claims (9)

In an H ₂ production apparatus that generates a gas containing hydrogen from fuel,
An ozone generator is provided at the front of the reformer, air or water is introduced into the ozone generator,
The ozone generated by the ozone generator, dissolved in H _{2 O} and / or fuel between the ozone generator and the reformer, H ₂ production apparatus characterized by introducing into the fuel reformer. In an H ₂ production apparatus that generates a gas containing hydrogen from fuel,
Equipped with an ozone generator (discharge type) at the front of the reformer, introducing air into the ozone generator,
The ozone generated by the ozone generator, dissolved in H _{2 O} between the ozone generator and the reformer, H ₂ production apparatus characterized by introducing into the reformer. In an H ₂ production apparatus that generates a gas containing hydrogen from fuel,
Equipped with an ozone generator (discharge type) at the front of the reformer, introducing air into the ozone generator,
An H ₂ production apparatus, wherein ozone generated by the ozone generator is dissolved in fuel between the ozone generator and the reformer and introduced into the reformer. In an H ₂ production apparatus that generates a gas containing hydrogen from fuel,
Equipped with an ozone generator (discharge type) at the front of the reformer, introducing air into the ozone generator,
The ozone generated by the ozone generator, dissolved in a mixed solution of fuel and water to and from the ozone generator and the reformer, H ₂ production apparatus characterized by introducing into the reformer. In H ₂ production apparatus according to claim 2-4, ozone from O ₃ containing gas coming out of the ozone generator to a portion of the O ₃ containing gas was dissolved in water and / or fuel to the reformer An H ₂ manufacturing apparatus that is introduced. In an H ₂ production apparatus that generates a gas containing hydrogen from fuel,
Equipped with an ozone generator (electrolytic) at the front of the reformer, water is introduced into the ozone generator,
The ozone generated by the ozone generator, dissolved in H _{2 O} between the ozone generator and the reformer, H ₂ production apparatus characterized by introducing into the reformer. In an H ₂ production apparatus that generates a gas containing hydrogen from fuel,
Equipped with an ozone generator (electrolytic) at the front of the reformer, water is introduced into the ozone generator,
An H ₂ production apparatus, wherein ozone generated by the ozone generator is dissolved in fuel between the ozone generator and the reformer and introduced into the reformer. In an H ₂ production apparatus that generates a gas containing hydrogen from fuel,
Equipped with an ozone generator (electrolytic) at the front of the reformer, water is introduced into the ozone generator,
The ozone generated by the ozone generator, is dissolved in the fuel and water to and from the ozone generator and the reformer, H ₂ production apparatus characterized by introducing into the reformer. In H ₂ production apparatus according to claim 6 to 8, the ozone from O ₃ containing gas coming out of the ozone generator to introduce O ₃ containing gas was dissolved in water and / or fuel to the reformer _{H 2} production apparatus according to claim.

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