JP5231857B2 - Oxidation autothermal reformer and solid oxide fuel cell system - Google Patents

Description

  The present invention relates to an oxidation autothermal reforming apparatus and a solid oxide fuel cell system including the same, and in particular, an oxidation capable of effectively raising the temperature of a reforming catalyst in a short time at the time of startup. A solid oxide fuel comprising an autothermal reformer and the oxidation autothermal reformer, and capable of maintaining the anode electrode side in a reduced state even when the oxidation autothermal reformer is started The present invention relates to a battery system.

  In a reformer that normally includes a reformer and supplies the reformer with a mixture of a reforming raw material and steam and causes a reforming reaction to generate a reformed gas mainly containing hydrogen, the reformer Before the reforming material is supplied to the reactor, it is necessary to start up the temperature inside the reformer to a temperature at which the reforming material can be reformed.

  For example, in a reformer employing a steam reforming method, a heating burner or the like is generally combined, and the reforming raw material is combusted outside the reformer to raise the temperature of the reformer (for example, Patent Document 1). reference). On the other hand, since the oxidation autothermal reformer does not have an external heat burner or the like, the temperature of the reformer is conventionally raised by an electric heater or the like, or the combustion gas of the reforming raw material is supplied to the interior of the reformer. It was starting up. However, when an electric heater or the like is used, it takes time to raise the temperature, and the outer surface of the reformer container may be partially heated. Further, a special combustor is required to send the combustion gas of the reforming raw material into the reformer, resulting in high cost and complicated apparatus. Furthermore, when the combustion gas is sent from the external combustor, the piping for sending the gas causes energy loss, the temperature of the gas is lowered, and it takes a long time to heat the reformer to the reforming temperature.

  In addition, a reforming fuel such as methanol and an oxidizing agent such as air are supplied to the reformer to cause a partial oxidation reaction by the catalyst. The temperature of the reformer is increased by the reaction heat at this time, and the partial oxidation reaction is performed. There has also been proposed a method in which the generated gas is further combusted in a combustor, the combustor is started at the same time as the reformer, and the reforming system is heated and started in a short time (see Patent Document 2). However, in this method, the reformed gas is supplied to the combustor during start-up, while the reformed gas is supplied to the fuel cell stack during steady operation. A control system for that purpose is required.

JP-A-11-86893 JP 2001-229953 A

  Accordingly, a first object of the present invention is to solve the above-mentioned problems of the prior art and to effectively raise the temperature of the reforming catalyst inside the reformer in a short time to a temperature at which the reforming raw material can be reformed. It is an object of the present invention to provide an oxidation autothermal reformer that can be used. The second object of the present invention is to provide a fuel cell system in which a solid oxide fuel cell is combined on the downstream side of an oxidation autothermal reformer, and at the start of temperature rising of the solid oxide fuel cell, the anode An object of the present invention is to provide a solid oxide fuel cell system capable of supplying a reducing gas to an anode electrode in a temperature range (usually 400 ° C. or higher) in which the electrode side needs to be reduced.

  As a result of diligent studies to achieve the above object, the present inventors have found that a substance that generates heat by an oxidation reaction (referred to as an oxidation exothermic substance) in an oxidation self-heating reformer having a reforming part and an oxidation heating part. And a line for introducing an oxidizing gas containing oxygen into the oxidation heat generating portion, and one end thereof is extended to the oxidation heat generation portion, In the oxidation exothermic part, a partial oxidation reaction is performed with a substance that generates heat by an oxidation reaction and an oxidizing gas containing oxygen to generate and / or remain a gas containing hydrogen and / or carbon monoxide. By raising the temperature of the reforming section to a temperature at which the reforming reaction can be performed by the generated heat, the oxidation self-heat reforming apparatus can be efficiently activated in a short time and generated and / or left. Hydrogen and / or carbon monoxide By supplying the contained gas to the anode electrode side of the solid oxide fuel cell, the anode electrode side can be maintained in a reducing atmosphere, and as a result, performance deterioration of the solid oxide fuel cell system can be suppressed. As a result, the present invention has been completed.

That is, the oxidation autothermal reformer of the present invention is at least partially filled with a reforming catalyst, and the reforming catalyst is at least one reforming selected from the group consisting of hydrocarbons or aliphatic alcohols. A reforming section that generates a reformed gas mainly composed of hydrogen by a reforming reaction by contacting a mixture of the raw material and steam, and at least a part of which is filled with an oxidation catalyst, the reformed raw material or the reformed gas An oxidation heat generating part that oxidizes a part of the heat generating part to generate heat, and the reforming part is disposed on the upstream side of the oxidation heat generating part,
Each of the reforming part and the oxidation heating part has a cylindrical shape, and the reforming part is composed of two layers of an inner reforming layer located on the radially inner side and an outer reforming layer located on the radially outer side. And the oxidation heat generating portion is disposed between the inner modified layer and the outer modified layer,
As means for supplying an oxidizing gas to the oxidation heat generating part, an oxidizing gas introduction line having one end extending to the oxidation heat generating part is installed,
Further, as a means for supplying a substance that generates heat due to an oxidation reaction to the oxidation heat generating portion, an oxidation heat generating material introduction line having one end extending to the oxidation heat generating portion is installed.

  The solid oxide fuel cell system of the present invention comprises the above oxidation autothermal reformer and a solid oxide fuel cell installed downstream of the oxidation autothermal reformer. It is characterized by.

  According to the oxidation autothermal reforming apparatus of the present invention, at the time of start-up, a substance that generates heat due to an oxidation reaction and an oxidizing gas containing oxygen are introduced into the oxidation heat generating portion of the oxidation autothermal reforming apparatus. By raising the temperature of the reforming section above the temperature at which the reforming reaction of the mixture of the reforming raw material and water vapor becomes possible due to oxidation heat generation, without using an external heater, etc., and in the oxidation autothermal reformer It is possible to start the oxidation autothermal reformer in a short time without damaging the catalyst.

  Further, in a solid oxide fuel cell system including an oxidation autothermal reformer and a solid oxide fuel cell, hydrogen and / or in the reaction gas in the oxidation autothermal reformer at startup A reducing gas containing hydrogen and / or carbon monoxide is supplied to the anode electrode side of the solid oxide fuel cell by performing a partial oxidation reaction under conditions where a gas containing carbon monoxide is generated and / or remains. In addition, it becomes possible to maintain the anode electrode side in a reducing atmosphere at the start of temperature rising of the solid oxide fuel cell, and as a result, the performance deterioration of the solid oxide fuel cell system is suppressed. be able to.

  Hereinafter, an embodiment of the present invention will be described in detail with reference to FIG. FIG. 1 is a schematic view of an example of a solid oxide fuel cell system equipped with an oxidation autothermal reformer of the present invention.

  The solid oxide fuel cell system shown in FIG. 1 includes an oxidation autothermal reformer 1 and a solid oxide fuel cell 2 installed downstream thereof. The oxidation autothermal reformer of the present invention is at least partially filled with a reforming catalyst, and the reforming catalyst includes at least one reforming raw material selected from the group consisting of hydrocarbons or aliphatic alcohols. A reforming section 1A that generates a reformed gas mainly composed of hydrogen by a reforming reaction by contacting with a mixture with water vapor, and at least a portion is filled with an oxidation catalyst. An oxidizing heat generating part 1B for oxidizing a part to generate heat is provided. Here, the reforming part 1A is arranged on the upstream side of the oxidizing heat generating part 1B.

  At least a part of the reforming section 1A is filled with a reforming catalyst, and the reforming catalyst is contacted with a mixture of at least one reforming raw material selected from the group consisting of hydrocarbons and aliphatic alcohols and steam. Thus, a reformed gas containing hydrogen as a main component is produced by the reforming reaction. Further, at least a part of the oxidation heat generating portion 1B is filled with an oxidation catalyst, and a part of the reforming raw material or the reformed gas is oxidized to generate heat.

  On the other hand, the solid oxide fuel cell of the solid oxide fuel cell system of the present invention is not particularly limited, and a solid oxide fuel cell having a known structure can be adopted. In general, the solid oxide fuel cell 2 is generally configured by stacking and / or connecting a plurality of cells.

  In addition, the solid oxide fuel cell of the present invention supplies an oxidizing gas to the oxidation heating unit 1B in addition to the raw material introduction line 3 being installed as a means for supplying the raw material to the reforming unit 1A. As a means for doing this, an oxidizing gas introduction line 4 having one end extending to the oxidation heat generating portion 1B is installed. Usually, at the time of the reforming reaction, at least one reforming material selected from the group consisting of hydrocarbon and aliphatic alcohol and water vapor are supplied to the reforming section 1A from the material introduction line 3, and an oxidizing gas is introduced. An oxidizing gas, particularly air, is introduced from the line 4 into the oxidation heat generating section 1B, the reforming reaction is performed in the reforming section 1A, the partial oxidation reaction is performed in the oxidizing heat generating section 1B, and the generated reformed gas is used as the anode fuel. It is supplied to the anode electrode of the solid oxide fuel cell 2 through the introduction line 5. At this time, air is supplied from the cathode air introduction line 6 to the cathode electrode of the solid oxide fuel cell 2 and the solid oxide fuel cell 2 performs electrochemical power generation. This power generation usually requires that the solid oxide fuel cell 2 be maintained at 700 to 1000 ° C. Note that hydrogen, carbon monoxide, nitrogen, and water and carbon dioxide generated by the power generation reaction that were supplied to the anode electrode but did not contribute to power generation are discharged from the anode exhaust gas outlet 7, while from the cathode exhaust gas outlet 8. Nitrogen and residual oxygen in the air that did not contribute to power generation are discharged.

  Here, in the oxidation autothermal reforming apparatus of the present invention, as described above, as the means for supplying the oxidizing gas to the oxidation heat generating portion 1B, an oxidizing gas introduction whose one end extends to the oxidation heat generating portion 1B is introduced. In addition to the line 4 being installed, an oxidation exothermic substance introduction line 9 having one end extending to the oxidation exothermic part 1B is installed as a means for supplying the oxidation exothermic part 1B with a substance that generates heat by an oxidation reaction. Has been. Therefore, in the oxidation autothermal reforming apparatus of the present invention, at the time of start-up, a substance that generates heat by the oxidation reaction is introduced from the oxidation exothermic substance introduction line 9 and an oxidizing gas containing oxygen from the oxidizing gas introduction line 4 is introduced. In order to perform partial oxidation reaction, the oxidation autothermal type can be effectively performed in a short time until the temperature of the reforming catalyst in the reforming section 1A becomes equal to or higher than the temperature at which the reforming raw material can be reformed. The reforming apparatus 1 can be started up at an elevated temperature. The target temperature of the reforming catalyst in the reforming unit 1A depends on the reforming raw material and is not particularly limited.

  As the substance that generates heat by the oxidation reaction, a gas containing hydrogen and / or carbon monoxide, a hydrocarbon and / or an aliphatic alcohol, and the like are preferable. Here, as the hydrocarbon, methane, ethane, propane, butane, Gases such as LP gas, natural gas, and city gas, and liquid fuels such as light oil, gasoline, naphtha, and kerosene can be used, and methanol, ethanol, and the like can be used as the aliphatic alcohol. Among these, in the present invention, a gaseous substance at room temperature, more specifically, a gas containing hydrogen and / or carbon monoxide, or a hydrocarbon having a small carbon number, that is, methane, ethane, propane, LP gas. Natural gas, city gas and the like are preferable. It is also possible to provide a reformer before the oxidation exothermic substance introduction line 9 and introduce at least one selected from the group consisting of the hydrocarbon and the aliphatic alcohol after once reformed. In such a case, a substance that is liquid at room temperature can also be suitably used. Of course, after the gaseous substance is reformed at room temperature, it can be introduced from the oxidation exothermic substance introduction line 9.

  On the other hand, as the oxidizing gas containing oxygen introduced from the oxidizing gas introduction line 4, pure oxygen gas can be used, but air is preferable from the viewpoint of cost and the like.

  Here, the introduction amounts of the oxidizing exothermic substance and the oxidizing gas can be changed as appropriate, but in the gas introduced into the solid oxide fuel cell 2 via the anode fuel introduction line 5, that is, the oxidation autothermal reforming. A reducing gas such as hydrogen or carbon monoxide needs to be present in the gas after the partial oxidation reaction inside the apparatus. When the substance that generates heat by the oxidation reaction contains hydrogen and / or carbon monoxide, the oxidation reaction is partially performed without complete oxidation to leave hydrogen and / or carbon monoxide. When the exothermic substance does not contain hydrogen and / or carbon monoxide, hydrogen and / or carbon monoxide is generated by a partial oxidation reaction.

  The total content of hydrogen and / or carbon monoxide in the gas after the partial oxidation reaction is not particularly limited as long as the gas after the partial oxidation reaction is in a reducing state. 0.5 volume% or more is preferable. If the total content of hydrogen and / or carbon monoxide in the gas after the partial oxidation reaction is too small, the reducing gas cannot reach the whole anode electrode of the solid oxide fuel cell, and the electrode may be partially oxidized. There is. In addition, in order to shorten the start-up time of the oxidation autothermal reformer, taking into account the reactivity of the oxidation catalyst, etc., it consumes as much oxygen as possible in a short time so that the calorific value of partial oxidation increases. It is preferable to proceed the reaction.

  Next, the oxidation autothermal reforming apparatus of the present invention will be described in more detail with reference to FIGS. 2 is a schematic view of a preferred example of the oxidation autothermal reformer of the present invention, FIG. 3 is a cross-sectional view taken along line III-III in FIG. 2, and FIG. It is sectional drawing which follows an IV line. This oxidation autothermal reformer has a cylindrical shape as a whole, and each element is formed in an annular shape and arranged concentrically.

  The illustrated oxidation self-heating reformer 10 includes a reforming layer 11 and an oxidation heat generation layer 12, and the modification layer 11 is located upstream of the oxidation heat generation layer 12. The modified layer 11 and the oxidation heat generating layer 12 each have a cylindrical shape. The modified layer 11 includes an inner modified layer 11A located on the radially inner side and an outer modified layer 11B located on the radially outer side. In addition to the two layers, an oxidation heat generation layer 12 is disposed between the inner modification layer 11A and the outer modification layer 11B, and the inner modification layer 11A, the oxidation heat generation layer 12, and the outer modification are formed from the radially inner side. A triple tube structure is arranged in the order of the layers 11B.

  Here, at least a part of the reforming layer 11 is filled with a reforming catalyst, and at least a part of the oxidation heat generation layer 12 is filled with an oxidation catalyst. As the reforming catalyst, a catalyst conventionally used for reforming can be used. For example, Ru, Ni, W, Co, Rh, Pt may be used alone or in plural on a support such as alumina, silica, zirconia. A supported one is used. Among these, particularly when kerosene is selected as the reforming raw material, a catalyst supporting Ru is preferable. Although a catalyst supporting Ru is generally low in oxidation resistance, it is excellent in reforming characteristics of a liquid fuel having a large number of carbon atoms. On the other hand, as the oxidation catalyst, a catalyst supporting Pt, Pd, Rh or the like which is not easily deteriorated at high temperature is preferable.

  The reforming layer 11 and the oxidation exothermic layer 12 include an inner cylinder 13 and an outer cylinder 14 of the oxidation autothermal reforming apparatus 10, and two tubular partition walls 15 (radial direction) positioned between the inner cylinder 13 and the outer cylinder 14. The inner partition wall 15A is separated from the radially outer partition wall 15B), and the space between the inner cylinder 13 and the radially inner partition wall 15A forms the inner modified layer 11A, and the radially inner partition wall 15A is separated from the inner partition wall 15A. A space between the radially outer partition walls 15B forms the oxidation heat generating layer 12, and a space between the radially outer partition walls 15B and the outer cylinder 14 forms the outer modified layer 11B. As shown in detail in FIG. 3, the inner cylinder 13, the radially inner partition 15 </ b> A, the radially outer partition 15 </ b> B, and the outer cylinder 14 form an annular and concentric circular tube structure. The inner modified layer 11A, the oxidation heat generating layer 12, and the outer modified layer 11B, which are respectively positioned therebetween, form a triple tube structure.

  Further, the oxidation autothermal reforming apparatus 10 shown in FIG. 2 includes a raw material introduction pipe 16 for supplying raw materials to both the inner reforming layer 11A and the outer reforming layer 11B, and reforming from the oxidation heat generation layer 12. A reformed gas discharge pipe 17 for discharging gas is connected to the lower portion of the outer cylinder 14. Partition receivers 18A, 18B, and 18C are disposed above the position where the raw material introduction pipe 16 is connected and below the inner modified layer 11A, the oxidation heat generating layer 12, and the outer modified layer 11B, respectively. The partition receivers 18A, 18B, and 18C allow a mixture of hydrocarbon or aliphatic alcohol and water vapor and reformed gas to pass through while preventing the catalyst or the like filled in each layer from falling. Further, a partition wall 19 is provided below the position where the raw material introduction pipe 16 is connected and above the position where the reformed gas discharge pipe 17 is connected. An opening 20 is provided in communication with.

  Furthermore, the oxidation self-heat reforming apparatus 10 in the illustrated example includes an oxidizing gas introduction line 21 that penetrates the upper end portion of the outer cylinder 14 to reach the oxidation heating layer 12, and is provided at the tip of the oxidizing gas introduction line 21. The tubular ring 22 is installed. Further, the tubular ring 22 is provided with a plurality of oxidizing gas ejection ports 23 as shown in FIG.

  Similarly, the oxidation self-heating reformer 10 of the illustrated example includes an oxidation exothermic substance introduction line 24 that penetrates the upper end portion of the outer cylinder 14 to reach the oxidation exothermic layer 12, and the tip of the oxidation exothermic substance introduction line 24. In addition, a tubular ring 25 is provided. The tubular ring 25 is also provided with a plurality of oxidizing exothermic material ejection ports 26 as shown in FIG.

  At the time of steady operation, the reforming raw material containing water vapor introduced from the raw material introduction pipe 16 in FIG. 2 into the raw material gas flow path 27 passes through the partition receivers 18A and 18C, and the inner reforming layer 11A and the outer reforming material. The reformed gas is reformed while flowing uniformly through the quality layer 11B, and becomes a reformed gas mainly composed of hydrogen. At this time, the heat required for the reforming is provided by the sensible heat generated by the oxidation heat generation occurring in the oxidation heat generating layer 12 being transmitted to the inner modified layer 11A and the outer modified layer 11B through the partition walls 15A and 15B.

  The reforming raw material introduced into the oxidation autothermal reforming apparatus 10 is partially or completely reformed in the inner reforming layer 11A and the outer reforming layer 11B, and becomes a reformed gas mainly composed of hydrogen. The reformed gas flow path 28 is entered. The C1 conversion rate at this time is usually 90% or more, although it varies depending on the reforming raw material and operating conditions.

  Further, the reformed gas returns and enters the oxidation heat generating layer 12 in a down flow. As described above, an oxidizing gas introduction line 21 is connected to the oxidation heat generating layer 12 as a means for supplying an oxidizing gas. A tubular ring 22 having a plurality of gas ejection ports 23 is provided. An oxidizing gas for oxidizing part of the reformed gas to generate heat is ejected from the plurality of oxidizing gas ejection ports 23 of the tubular ring 22 through the oxidizing gas introduction line 21. Here, as the kind of oxidizing gas to be used, pure oxygen can be used, but it is generally preferable to use air from the viewpoint of cost.

  In the oxidation exothermic layer 12, in order to supplement the endothermic heat in the inner reforming layer 11A and the outer reforming layer 11B, the oxidation reaction between hydrogen, methane, etc. in the reformed gas introduced into the oxidation exothermic layer 12 and the oxidizing gas. It is essential to perform (exothermic reaction), and the oxidation reaction is promoted by an oxidation catalyst.

  First, the oxidation heat generating layer 12 can be filled with a mixture of an oxidation catalyst and a reforming catalyst. Here, the reforming catalyst used for the oxidation exothermic layer 12 further reforms methane and / or C2 + components (components having 2 or more carbon atoms) remaining in the reformed gas led to the oxidation exothermic layer 12. The endotherm for this reforming is directly covered by the heat generated by the oxidation reaction promoted by the mixed oxidation catalyst, creating a state in which reforming and oxidation proceed simultaneously. .

  Secondly, the oxidation heat generating layer 12 can be filled with a mixture of an oxidation catalyst and heat transfer particles. In the oxidation heat generating layer 12, the temperature immediately below the outlet of the oxidizing gas tends to be the highest, and the temperature decreases as it goes downstream. Therefore, by using a part of the heat transfer particles in the oxidation heat generation layer 12, the temperature difference between the upstream side and the downstream side of the oxidation heat generation layer 12 can be reduced. Here, the heat transfer particles transfer heat generated by the oxidation reaction to the entire oxidation exothermic layer 12, thereby upstream of the inner reforming layer 11A and the outer reforming layer 11B adjacent to the oxidation exothermic layer 12. On the side, the amount of heat transfer through the tubular partition walls 15A and 15B increases, and the temperature difference between the upstream and downstream sides of the inner modified layer 11A and the outer modified layer 11B can be reduced.

  Furthermore, thirdly, the oxidation heat generating layer 12 can be filled with a mixture of an oxidation catalyst, a reforming catalyst, and heat transfer particles. In this case, the oxidation heat generating layer 12 exhibits the effect of the second case in the first case described above.

  As the reforming catalyst used for the oxidation exothermic layer 12, the reforming catalyst used for the reforming layer 11 can be used. However, since the oxidation exothermic layer 12 is in an oxidizing atmosphere, Ni and Rh are used alone. Alternatively, a plurality of supported catalysts are preferable. In addition, the material of the heat transfer particles used for the oxidation heat generation layer 12 is not particularly defined, but a material having higher thermal conductivity is preferable, and porous silicon carbide particles are preferable.

  The installation position of the tubular ring 22 for ejecting the oxidizing gas and the tubular ring 25 for ejecting the oxidizing exothermic material is preferably relatively upper in the oxidizing exothermic layer 12, but is not particularly limited. Considering the direction of heat transfer, a position higher than the inner modified layer 11A and the outer modified layer 11B is preferable. The upper and lower sides of the tubular rings 22 and 25 can be filled with the same mixture, but different ones can be filled.

The amount of oxidizing gas supplied to the oxidizing heat generating layer 12 from the tubular ring 22 for ejecting oxidizing gas varies depending on the type of reforming raw material, but the oxygen / carbon ratio (O ₂ / C) = 0. About 1 to 0.5 is preferable. Thereby, the highest temperature part of the oxidation heat_generation | fever layer 12 will be about 650-850 degreeC. Therefore, it is not necessary to use a particularly expensive material for the oxidation autothermal reformer.

  The reformed gas partially oxidized and / or reformed in the oxidation heat generation layer 12 passes through the partition receiver 18B, is guided to the reformed gas flow path 29, and is discharged from the reformed gas discharge pipe 17. . Thereafter, the discharged reformed gas can be supplied to the solid oxide fuel cell 2 as it is.

  In addition, in the oxidation self-heat reforming apparatus of the present invention, at the time of start-up, an oxidizing gas containing oxygen is introduced into the oxidizing heat generating layer 12 in FIG. A gas containing heat and / or carbon monoxide can be generated and / or left by introducing a substance that generates heat by an oxidation reaction into the layer 12 via the oxidation exothermic substance introduction line 24 and causing a partial oxidation reaction. Here, the reforming layer 11 is heated by the oxidation heat generated by the partial oxidation reaction in the oxidation exothermic layer 12, and the reforming layer 11 is brought to a temperature higher than the temperature at which the reforming reaction of the mixture of the reforming raw material and water vapor becomes possible. The temperature can be raised. In addition, according to the oxidation autothermal reforming apparatus of the present invention, a gas containing hydrogen and / or carbon monoxide can be generated and / or left by a partial oxidation reaction, so that the gas passes through the partition receiver 18B. Hydrogen and / or carbon monoxide can be included in the gas guided to the reformed gas flow path 29 and discharged from the reformed gas discharge pipe 17. Therefore, by using the oxidation autothermal reforming apparatus of the present invention and including hydrogen and / or carbon monoxide in the gas discharged from the reformed gas discharge pipe 17 at the start-up, the reformed gas discharge pipe Even if the gas discharged from 17 is directly supplied to the anode electrode side, the anode electrode side can be maintained in a reducing atmosphere, and the performance deterioration of the solid oxide fuel cell 2 can be suppressed.

  2 to 4, the raw material gas is introduced from the lower part of the reformer, the oxidizing gas and the oxidizing exothermic substance are separately introduced from the upper part of the reformer, and the reforming is performed from the lower part of the reformer. However, the oxidizing autothermal reforming apparatus of the present invention is not limited to this. For example, the raw material gas is introduced from the upper part of the reforming apparatus, and the oxidizing gas is introduced from the lower part of the reforming apparatus. In addition, the oxidation exothermic substance may be separately introduced, and the reformed gas may be discharged from the upper part of the reformer.

It is the schematic of an example of the solid oxide fuel cell system provided with the oxidation autothermal reformer of this invention. It is the schematic of an example of the oxidation autothermal reforming apparatus of this invention. It is sectional drawing which follows the III-III line of FIG. It is sectional drawing which follows the IV-IV line of FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Oxidation autothermal reformer 1A Reforming part 1B Oxidation heat generation part 2 Solid oxide fuel cell 3 Raw material introduction line 4,21 Oxidizing gas introduction line 5 Anode fuel introduction line 6 Cathode air introduction line 7 Anode exhaust gas outlet 8 Cathode exhaust gas outlet 9, 24 Oxidation exothermic substance introduction line 10 Oxidation autothermal reformer 11 Modification layer 11A Inner modification layer 11B Outer modification layer 12 Oxidation exothermic layer 13 Inner cylinder 14 Outer cylinder 15 Tubular partition 15A Radial inner side Partition wall 15B radially outer partition wall 16 raw material introduction pipe 17 reformed gas discharge pipe 18A, 18B, 18C partition receiver 19 partition wall 20 opening 22, 25 tubular ring 23 oxidizing gas ejection port 26 oxidizing exothermic material ejection port 27 raw material Gas flow path 28, 29 Reformed gas flow path

Claims (2)

At least a part of the reforming catalyst is filled, and the reforming catalyst is brought into contact with a mixture of at least one reforming raw material selected from the group consisting of hydrocarbons or aliphatic alcohols and steam to generate hydrogen by reforming reaction. A reforming section for generating a reformed gas containing as a main component, and an oxidation heating section for generating heat by oxidizing at least a part of the reforming raw material or the reformed gas, at least partially filled with an oxidation catalyst And the reforming part is disposed on the upstream side of the oxidation heat generating part,
Each of the reforming part and the oxidation heating part has a cylindrical shape, and the reforming part is composed of two layers of an inner reforming layer located on the radially inner side and an outer reforming layer located on the radially outer side. And the oxidation heat generating portion is disposed between the inner modified layer and the outer modified layer,
As means for supplying an oxidizing gas to the oxidation heat generating part, an oxidizing gas introduction line having one end extending to the oxidation heat generating part is installed,
In addition, as a means for supplying a substance that generates heat by an oxidation reaction to the oxidation heat generating portion, an oxidation heat generating material introduction line having one end extending to the oxidation heat generating portion is installed. Reformer.   A solid oxide fuel cell system comprising: the oxidation autothermal reformer according to claim 1; and a solid oxide fuel cell installed downstream of the oxidation autothermal reformer.

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