WO2013042314A1 - Process for generating hydrogen-containing gas and method for operating fuel cell system - Google Patents

Process for generating hydrogen-containing gas and method for operating fuel cell system Download PDF

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WO2013042314A1
WO2013042314A1 PCT/JP2012/005305 JP2012005305W WO2013042314A1 WO 2013042314 A1 WO2013042314 A1 WO 2013042314A1 JP 2012005305 W JP2012005305 W JP 2012005305W WO 2013042314 A1 WO2013042314 A1 WO 2013042314A1
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reforming catalyst
catalyst
reforming
hydrogen
containing gas
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PCT/JP2012/005305
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French (fr)
Japanese (ja)
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藤原　誠二
中嶋　知之
脇田　英延
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パナソニック株式会社
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    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/384—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts the catalyst being continuously externally heated
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
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    • H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
    • H01M8/0625—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material in a modular combined reactor/fuel cell structure
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    • C01B2203/08—Methods of heating or cooling
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    • C01B2203/1041—Composition of the catalyst
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    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
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    • C01B2203/1288—Evaporation of one or more of the different feed components
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    • C01B2203/16—Controlling the process
    • C01B2203/1614—Controlling the temperature
    • C01B2203/1623—Adjusting the temperature
    • H—ELECTRICITY
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    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
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    • H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
    • H01M8/0618—Reforming processes, e.g. autothermal, partial oxidation or steam reforming
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the present invention relates to a method for generating a hydrogen-containing gas and a method for operating a fuel cell system.
  • the raw material contains at least an organic compound having carbon and hydrogen as constituent elements.
  • the raw material gas include city gas mainly composed of methane, natural gas, and LPG.
  • a CO reducer for reducing carbon monoxide in the hydrogen-containing gas produced by the reforming reaction may be provided.
  • the CO reducer includes at least one of a transformer that reduces carbon monoxide by a shift reaction and a CO remover that reduces carbon monoxide by at least one of an oxidation reaction and a methanation reaction.
  • the raw material when the raw material contains nitrogen-containing compounds such as nitrogen molecules and amines, it reacts with hydrogen produced by the reforming reaction to produce ammonia, which is used as a catalyst for CO removers, fuel cells, etc. It is known to become a poison (see, for example, Patent Document 1).
  • the present invention solves the above-described conventional problems, and an object of the present invention is to provide a method for producing a hydrogen-containing gas and a method for operating a fuel cell system, which suppress the production of ammonia as compared with the conventional art.
  • a method for producing a hydrogen-containing gas of one embodiment of the present invention includes a step of passing a raw material containing at least one of nitrogen molecules and a nitrogen-containing compound through a first reforming catalyst, And a step of passing a second reforming catalyst that is disposed downstream of the first reforming catalyst and has a lower catalytic ability per unit amount for the reforming reaction than the first reforming catalyst.
  • the method for producing a hydrogen-containing gas of one embodiment of the present invention it is possible to produce a hydrogen-containing gas while suppressing the production of ammonia as compared with the conventional method.
  • FIG. 1 is a diagram illustrating an example of a schematic configuration of a reformer used in the method for generating a hydrogen-containing gas according to the first embodiment.
  • FIG. 2 is a diagram showing an example of an experimental result comparing the catalytic ability of the reforming catalyst.
  • FIG. 3 is a diagram illustrating an example of a schematic configuration of a fuel cell system used in the operation method of the fuel cell system according to the second embodiment.
  • the downstream catalyst having a relatively small amount of reforming reaction has a relatively higher temperature than the upstream catalyst. As the temperature increases, the amount of ammonia produced increases in terms of reaction rate.
  • the raw material containing at least one of nitrogen molecules and nitrogen-containing compounds is passed through the first reforming catalyst, and the first reforming catalyst is used. And a step of passing a second reforming catalyst which is disposed downstream and has a lower catalytic ability per unit amount for the reforming reaction than the first reforming catalyst.
  • the catalytic ability means the ability to catalyze the reforming reaction.
  • FIG. 1 is a diagram illustrating an example of a schematic configuration of a reformer used in the method for producing a hydrogen-containing gas according to the first embodiment.
  • the reformer 100 generates a hydrogen-containing gas using a raw material containing at least one of nitrogen molecules and nitrogen-containing compounds.
  • the raw material gas undergoes a reforming reaction to generate a hydrogen-containing gas.
  • the reforming reaction may take any form, and examples thereof include a steam reforming reaction, an autothermal reaction, and a partial oxidation reaction.
  • equipment required for each reforming reaction is provided as appropriate.
  • the reforming reaction is a steam reforming reaction
  • a combustor that heats the reformer 100
  • an evaporator that generates steam
  • a water supplier that supplies water to the evaporator
  • the reformer 100 is further provided with an air supply device that supplies air to the reformer 100.
  • the raw material contains at least an organic compound containing carbon and hydrogen as constituent elements.
  • Examples of the raw material include city gas mainly composed of methane, natural gas, and LPG.
  • Examples of the nitrogen-containing compound include amines and isonitriles.
  • a CO reducer for reducing carbon monoxide in the hydrogen-containing gas produced by the reformer 100 may be provided downstream of the reformer 100.
  • the CO reducer includes at least one of a transformer that reduces carbon monoxide by a shift reaction and a CO remover that reduces carbon monoxide by at least one of an oxidation reaction and a methanation reaction.
  • the reformer 100 includes a first reforming catalyst 1 and a second reforming catalyst 2 disposed downstream of the first reforming catalyst 1.
  • Each of the first reforming catalyst 1 and the second reforming catalyst 2 includes a catalyst metal and a catalyst metal carrier.
  • the second reforming catalyst 2 has a lower catalytic ability per unit amount for the reforming reaction than the first reforming catalyst 1. If this is satisfied, the first reforming catalyst 1 and the second reforming catalyst 2 may be in any form, but specific examples will be described in the following examples.
  • the unit amount includes, for example, a unit weight, a unit volume, and a mole, but is not limited to these, and any unit amount may be used as long as it is a general unit amount.
  • a raw material containing at least one of nitrogen molecules and nitrogen-containing compounds is supplied to the reformer 100 to generate a hydrogen-containing gas.
  • the step of passing the source gas through the first reforming catalyst 1 having a relatively high catalytic ability per unit amount for the reforming reaction And a step of passing a second reforming catalyst 2 disposed downstream of the reforming catalyst 1 and having a relatively low catalytic ability per unit amount for the reforming reaction.
  • the second reforming catalyst 2 since the reforming reaction of the reforming catalyst is an endothermic reaction, the second reforming catalyst 2 having a smaller amount of reforming reaction than the first reforming catalyst 1 The temperature is likely to be higher than that of the reforming catalyst 1.
  • FIG. 1 it is comprised so that the 2nd reforming catalyst 2 and the 1st reforming catalyst 1 may be heated in order by the high-temperature combustion exhaust gas. 2 is higher in temperature than the first reforming catalyst 1.
  • the second reforming catalyst 2 is more likely to increase the amount of ammonia produced in terms of the reaction rate than the first reforming catalyst 1.
  • Example 1 In Example 1, the content of the catalyst metal per unit volume of the second reforming catalyst is less than that of the first reforming catalyst, so that the second reforming catalyst 2 The catalytic ability per unit amount for the reforming reaction is lower than that of the reforming catalyst 1.
  • the method for generating a hydrogen-containing gas of the present embodiment includes a step of passing a raw material containing at least one of nitrogen molecules and a nitrogen-containing compound through the first reforming catalyst, and more than the first reforming catalyst. And passing a second reforming catalyst disposed downstream and having a catalytic metal content per unit volume less than that of the first reforming catalyst.
  • FIG. 2 is a diagram showing an example of an experimental result comparing the catalytic performance of the reforming catalyst.
  • the reforming catalyst includes a catalyst metal containing Ru and an alumina support as a support for the catalyst metal.
  • FIG. 2 shows the experimental results of examining the difference in catalytic ability for the reforming reaction due to the difference in the content of the catalytic metal per unit volume of the reforming catalyst.
  • a reforming catalyst (hereinafter sometimes abbreviated as “2 wt% Ru / alumina catalyst”) having a Ru loading on the alumina support of 2 wt%, and a Ru loading on the alumina support of 0.5 wt%.
  • the reforming catalyst (hereinafter sometimes abbreviated as “0.5 wt% Ru / alumina catalyst”) was prepared.
  • FIG. 2 shows the relationship between the temperature (° C.) of the reforming catalyst and the methane (CH 4 ) conversion rate (%) representing the catalytic ability of the reforming catalyst.
  • the fixed bed flow type reactor was filled with 0.6 cc of 2 wt% Ru / alumina catalyst and 0.5 wt% Ru / alumina catalyst, respectively, so that the methane flow rate was 100 ml / min. Water is supplied so that the water flow rate is 0.201 g / min. In this case, SV is 10,000 / h. Further, the reforming catalyst is heated using an electric furnace to adjust the temperature of the reforming catalyst, and the methane conversion rate is derived by measuring the concentration of the outlet gas of the reforming catalyst by gas chromatography.
  • the 2 wt% Ru / alumina catalyst always has a higher methane conversion rate than the 0.5 wt% Ru / alumina catalyst. That is, a 2 wt% Ru / alumina catalyst having a relatively high content of catalytic metal per unit volume has a relatively high catalytic ability per unit amount for the reforming reaction. On the other hand, a 0.5 wt% Ru / alumina catalyst having a relatively small content of catalytic metal per unit volume has a relatively low catalytic ability per unit amount for the reforming reaction.
  • the temperature of the first reforming catalyst 1 is, for example, 400
  • the temperature of the second reforming catalyst 2 is adjusted to about 600 ° C.
  • the source gas contains at least one of nitrogen molecules and nitrogen-containing compounds
  • ammonia is generated as the reforming reaction of the source gas proceeds, and the amount of ammonia generated greatly depends on the temperature of the reforming catalyst.
  • a 2 wt% Ru / alumina catalyst has an ammonia production amount of 1 ppm or less under the condition that the temperature of the reforming catalyst is 400 ° C. At 600 ° C., it becomes about 10 ppm.
  • the amount of ammonia produced can be suppressed to about 1 ppm even at 600 ° C.
  • the 2 wt% Ru / alumina catalyst which has a relatively high catalytic capacity per unit amount for the reforming reaction, has a high ability to catalyze the reaction for generating ammonia. It is preferred to use the catalyst at a low temperature.
  • a 0.5 wt% Ru / alumina catalyst having a relatively low catalytic ability per unit amount for the reforming reaction can suppress an ammonia production amount even at a high temperature.
  • a 2 wt% Ru / alumina catalyst is used for the first reforming catalyst 1 and a 0.5 wt% Ru / alumina catalyst is used for the second reforming catalyst 2. Therefore, the method for producing the hydrogen-containing gas of the present embodiment can produce the hydrogen-containing gas while suppressing the production of ammonia as compared with the conventional method.
  • the above Ru as the catalyst metal of the first reforming catalyst 1 and the second reforming catalyst 2 is an example, and the catalyst metal of the first reforming catalyst 1 and the second reforming catalyst 2 is an example. Any catalyst metal can be used as long as it can cause the reforming reaction to proceed, and the present invention is not limited to this example.
  • the catalyst metals of the first reforming catalyst 1 and the second reforming catalyst 2 are generally selected from the group consisting of noble metal catalysts such as Pt, Ru, Rh, Pd, and Ni-based catalysts. At least one kind can be suitably used.
  • the catalyst metal of the first reforming catalyst 1 and the second reforming catalyst 2 may be the same metal species or different metal species.
  • the second catalytic metal has a catalytic ability for the reforming reaction equal to or lower than that of the first catalytic metal. It becomes.
  • the above-mentioned alumina carrier as the carrier of the first reforming catalyst 1 and the second reforming catalyst 2 is an example, and the carrier of the first reforming catalyst 1 and the second reforming catalyst 2 is However, the present invention is not limited to this example.
  • the catalyst metal carrier of the first reforming catalyst 1 and the second reforming catalyst 2 may be any carrier as long as it can carry the catalyst metal.
  • the above-mentioned Ru loadings of the first reforming catalyst 1 and the second reforming catalyst 2 are examples, and per unit volume of the first reforming catalyst 1 and the second reforming catalyst 2.
  • the content of the catalyst metal is not limited to this example.
  • first reforming catalyst 1 and the second reforming catalyst 2 are merely examples, and these are not limited to this example.
  • Ru-based reforming catalysts are generally poisoned with sulfur, if the source gas contains sulfur, an adsorptive desulfurizing agent or hydrodesulfurizing agent is provided in the front stage of the reforming catalyst to remove sulfur. Yes. However, it is difficult to completely remove sulfur, and about several ppb may be supplied to the reforming catalyst. Therefore, as described above, when the first reforming catalyst 1 is filled with a catalyst having a relatively high catalytic capacity for the reforming reaction, the performance of the reforming reaction is hardly lowered even if sulfur is supplied. This is advantageous in terms of catalyst durability.
  • Example 2 since sulfur is trapped by the first reforming catalyst 1, even if the second reforming catalyst 2 has a catalyst having a relatively low catalytic ability for the reforming reaction, the performance of the reforming reaction by sulfur. Reduction can be suppressed.
  • the specific surface area of the second reforming catalyst is made smaller than that of the first reforming catalyst, so that the second reforming catalyst 2 is modified more than the first reforming catalyst 1. The catalytic ability per unit amount for the quality reaction is low.
  • the method for generating a hydrogen-containing gas of the present embodiment includes a step of passing a raw material containing at least one of nitrogen molecules and a nitrogen-containing compound through the first reforming catalyst, and more than the first reforming catalyst. And passing a second reforming catalyst disposed downstream and having a specific surface area smaller than that of the first reforming catalyst.
  • both the first reforming catalyst and the second reforming catalyst include a catalyst metal containing Ru and an alumina support as a catalyst metal support.
  • a quality catalyst is disposed downstream of the first reforming catalyst.
  • the specific surface area of the second reforming catalyst is smaller than the specific surface area of the first reforming catalyst.
  • a reforming catalyst having a large specific surface area has a higher catalytic ability for the reforming reaction.
  • the second reforming catalyst 2 having a specific surface area smaller than that of the first reforming catalyst 1 is relatively lower in catalytic ability per unit amount for the reforming reaction than the first reforming catalyst 1. .
  • a raw material containing at least one of nitrogen molecules and a nitrogen-containing compound is passed through a reformer including the first reforming catalyst 1 and the second reforming catalyst 2 to advance the reforming reaction.
  • a reformer including the first reforming catalyst 1 and the second reforming catalyst 2 to advance the reforming reaction.
  • a hydrogen-containing gas is produced.
  • the method for producing a hydrogen-containing gas according to the present embodiment can produce a hydrogen-containing gas while suppressing the production of ammonia as compared with the conventional method.
  • the above Ru as the catalyst metal of the first reforming catalyst 1 and the second reforming catalyst 2 is an example, and the catalyst metal of the first reforming catalyst 1 and the second reforming catalyst 2 is an example. Any catalyst metal can be used as long as it can cause the reforming reaction to proceed, and the present invention is not limited to this example.
  • the catalyst metals of the first reforming catalyst 1 and the second reforming catalyst 2 are generally selected from the group consisting of noble metal catalysts such as Pt, Ru, Rh, Pd, and Ni-based catalysts. At least one kind can be suitably used.
  • the catalyst metal of the first reforming catalyst 1 and the second reforming catalyst 2 may be the same metal species or different metal species.
  • the second catalytic metal has a catalytic ability for the reforming reaction equal to or lower than that of the first catalytic metal. It becomes.
  • the above-mentioned alumina carrier as the carrier of the first reforming catalyst 1 and the second reforming catalyst 2 is an example, and the carrier of the first reforming catalyst 1 and the second reforming catalyst 2 is However, the present invention is not limited to this example.
  • the catalyst metal carrier of the first reforming catalyst 1 and the second reforming catalyst 2 may be any carrier as long as it can carry the catalyst metal.
  • the second carrier carrying the catalyst metal contained in the second reforming catalyst is more suitable for the reforming reaction than the first carrier carrying the catalyst metal contained in the first reforming catalyst. The effect is low. As a result, the second reforming catalyst 2 has a lower catalytic ability per unit amount for the reforming reaction than the first reforming catalyst 1.
  • the method for generating a hydrogen-containing gas of the present embodiment includes a step of passing a raw material containing at least one of nitrogen molecules and a nitrogen-containing compound through the first reforming catalyst, and more than the first reforming catalyst. And passing a second reforming catalyst disposed downstream and having a carrier effect smaller than that of the first reforming catalyst.
  • first reforming catalyst and the second reforming catalyst are provided with the same catalyst metal.
  • both the first reforming catalyst and the second reforming catalyst include a catalyst metal containing Ru.
  • the first carrier supporting the catalyst metal included in the first reforming catalyst and the second carrier supporting the catalyst metal included in the second reforming catalyst Different from the carrier.
  • the second carrier has a lower carrier effect on the reforming reaction than the first carrier.
  • a zirconia support rather than an alumina support has a lower support effect on the reforming reaction. Therefore, in this embodiment, an alumina carrier having a high carrier effect is used for the first reforming catalyst 1, and a zirconia carrier having a low carrier effect is used for the second reforming catalyst 2.
  • the second reforming catalyst including the second carrier having a smaller carrier effect than the first carrier has a lower catalytic ability per unit amount relative to the reforming reaction than the first reforming catalyst.
  • the first reforming catalyst 1 and the second reforming catalyst 2 each including the first carrier and the second carrier include a raw material containing at least one of a nitrogen molecule and a nitrogen-containing compound. And a reforming reaction proceeds to produce a hydrogen-containing gas.
  • the method for producing a hydrogen-containing gas according to the present embodiment can produce a hydrogen-containing gas while suppressing the production of ammonia as compared with the conventional method.
  • the above Ru as the catalyst metal of the first reforming catalyst 1 and the second reforming catalyst 2 is an example, and the catalyst metal of the first reforming catalyst 1 and the second reforming catalyst 2 is an example. Any catalyst metal can be used as long as it can cause the reforming reaction to proceed, and the present invention is not limited to this example.
  • the catalyst metal of the first reforming catalyst 1 and the second reforming catalyst 2 is generally at least one selected from the group consisting of noble metal catalysts such as Pt, Ru, Rh, Pd, and Ni-based catalysts. Species can be suitably used.
  • the catalyst metal of the first reforming catalyst 1 and the second reforming catalyst 2 may be the same metal species or different metal species.
  • the second catalytic metal has a catalytic ability for the reforming reaction equal to or lower than that of the first catalytic metal. It becomes.
  • the above-described alumina carrier and zirconia carrier as carriers for the first reforming catalyst 1 and the second reforming catalyst 2 are examples, and the first reforming catalyst 1 and the second reforming catalyst 2 are examples.
  • the carrier is not limited to this example.
  • the carrier of the catalyst metal of the first reforming catalyst 1 and the second reforming catalyst 2 may be any carrier as long as it satisfies the above-described level of the carrier effect and can carry the catalyst metal. .
  • the first reforming catalyst and the second reforming catalyst are catalysts containing Ni as a catalyst metal.
  • the content of the catalyst metal per unit volume of the second reforming catalyst is less than that of the first reforming catalyst 1, so that the second The reforming catalyst 2 has a lower catalytic ability per unit amount for the reforming reaction than the first reforming catalyst 1.
  • the first reforming catalyst and the second reforming catalyst both include a catalyst metal containing Ni and an alumina carrier as a carrier for the catalyst metal, and the second reforming catalyst is the first reforming catalyst. Is disposed downstream of the reforming catalyst.
  • the first reforming catalyst is configured so that the content of the catalytic metal per unit volume is relatively larger than that of the second reforming catalyst.
  • the first reforming catalyst 1 a reforming catalyst having a supported amount of catalytic metal containing Ni in an alumina carrier of 30 wt% is used, and as the second reforming catalyst 2, A reforming catalyst in which the supported amount of the catalyst metal containing Ni on the alumina support is 20 wt% is used.
  • the reforming catalyst having a higher content of catalytic metal containing Ni per unit volume has a higher methane conversion rate. That is, the catalytic ability for the reforming reaction is high.
  • the second reforming catalyst 2 having a lower catalyst metal content per unit volume than the first reforming catalyst 1 has a relatively low catalytic ability per unit amount for the reforming reaction.
  • the method for producing a hydrogen-containing gas according to the present embodiment can produce a hydrogen-containing gas while suppressing the production of ammonia as compared with the conventional method.
  • the above-mentioned alumina carrier as the carrier of the first reforming catalyst 1 and the second reforming catalyst 2 is an example, and the carrier of the first reforming catalyst 1 and the second reforming catalyst 2 is However, the present invention is not limited to this example.
  • the catalyst metal carrier of the first reforming catalyst 1 and the second reforming catalyst 2 may be any carrier as long as it can carry the catalyst metal.
  • the above-mentioned amount of Ni supported by the first reforming catalyst 1 and the second reforming catalyst 2 is an exemplification, and per unit volume of the first reforming catalyst 1 and the second reforming catalyst 2.
  • the content of the catalyst metal is not limited to this example.
  • the content of the catalyst metal per unit volume of the second reforming catalyst is less than that of the first reforming catalyst 1, so that the second The reforming catalyst 2 has lower catalytic ability per unit amount for the reforming reaction than the first reforming catalyst 1, but is not limited thereto.
  • Example 5 A method for producing the hydrogen-containing gas of Example 5 will be described.
  • the first reforming catalyst and the second reforming catalyst are divided.
  • the first reforming catalyst 1 can be filled upstream of the reformer 100. Further, the second reforming catalyst 2 can be filled on the downstream side of the reformer 100.
  • a partition member (not shown) for partitioning the first reforming catalyst 1 and the second reforming catalyst 2 may be provided. A plurality of holes that do not allow the reforming catalyst to pass through the gas may be formed in the partition member.
  • the above-described divided arrangement of the first reforming catalyst 1 and the second reforming catalyst 2 is an example, and the form of arrangement of the first reforming catalyst 1 and the second reforming catalyst 2 is as follows. It is not limited to this example. If the above-described high / low relation of the catalytic ability is satisfied between the first reforming catalyst 1 and the second reforming catalyst 2, how the first reforming catalyst 1 and the second reforming catalyst 2 are arranged. May be.
  • the first reforming catalyst 1 and the second reforming catalyst 2 are mixed, and the concentration of the first reforming catalyst decreases toward the downstream.
  • it may be in the form of an arrangement having a concentration gradient.
  • the amount of the second reforming catalyst is larger than that of the first reforming catalyst.
  • the method for generating a hydrogen-containing gas of the present embodiment includes a step of passing a raw material containing at least one of nitrogen molecules and a nitrogen-containing compound through the first reforming catalyst, and more than the first reforming catalyst.
  • a second reforming catalyst disposed downstream and passing a second reforming catalyst having a catalytic capacity for the reforming reaction that is smaller than that of the first reforming catalyst, wherein the second reforming catalyst is a first reforming catalyst. More catalyst than
  • the first reforming catalyst 1 and the second reforming catalyst 2 provided in the reformer 100 are converted into the second reforming catalyst 2 by any one of the methods in Embodiment 1-5.
  • the catalytic performance per unit amount for the reforming reaction is lower than that of the first reforming catalyst 1.
  • the second reforming catalyst has a larger amount of catalyst than the first reforming catalyst.
  • the methane conversion rate tends to be lower than the equilibrium, but the amount of the second reforming catalyst 2 is increased to increase SV. Is preferable because the methane conversion rate approaches equilibrium.
  • the first reforming catalyst 1 may be charged to a position close to the high temperature region on the downstream side of the reformer 100. In this case, there is a possibility that the first reforming catalyst 1 is used in a high temperature state, and ammonia is easily generated in the first reforming catalyst 1.
  • the second reforming catalyst 2 has a larger amount of catalyst than the first reforming catalyst 1.
  • the first reforming catalyst 1 and the second reforming catalyst are set so that the ratio between the catalyst amount of the first reforming catalyst 1 and the catalyst amount of the second reforming catalyst 2 is, for example, 1: 2. 2 may be charged into the reformer 100, or the amount of the second reforming catalyst 2 may be further increased. However, considering the cost reduction and compactness of the reformer, the above ratio is preferably about 1: 2 to 1: 5. [Example 7] In Example 7, the catalytic capacity for the reforming reaction of the catalyst metal included in the second reforming catalyst is made lower than that of the catalyst metal included in the first reforming catalyst, whereby the second reforming catalyst 2 Is lower in catalytic ability per unit amount than the first reforming catalyst 1 for the reforming reaction.
  • the method for generating a hydrogen-containing gas of the present embodiment includes a step of passing a raw material containing at least one of nitrogen molecules and a nitrogen-containing compound through the first reforming catalyst, and more than the first reforming catalyst. And a step of passing a second reforming catalyst disposed downstream and having a catalytic ability for the reforming reaction of the catalytic metal lower than that of the first reforming catalyst.
  • a specific example of the method for generating the hydrogen-containing gas of Example 7 will be described in detail.
  • the reforming catalyst has higher catalytic ability for the reforming reaction in the order of Ru catalyst, Ru—Pt composite catalyst, Ni catalyst, and Pt—Rh composite catalyst under the same use conditions.
  • the first reforming catalyst 1 is the second reforming catalyst 1 based on the relation of the catalytic ability to the reforming reaction of Ru catalyst> Ru—Pt composite catalyst> Ni catalyst> Pt—Rh composite catalyst.
  • the reforming catalyst is appropriately selected so that the catalytic ability for the reforming reaction is higher than that of the reforming catalyst 2.
  • a combination using a Ru catalyst as the first reforming catalyst 1 and a Pt—Rh composite catalyst as the second reforming catalyst 2 is excluded.
  • a Ru catalyst may be used as the first reforming catalyst 1, and a Ni catalyst may be used as the second reforming catalyst 2. Further, a Ru catalyst may be used as the first reforming catalyst 1, and a Pt catalyst may be used as the second reforming catalyst 2. Further, a Ru—Pt composite catalyst may be used as the first reforming catalyst 1, and a Pt—Rh composite catalyst may be used as the second reforming catalyst 2.
  • the combination of the above reforming catalysts is an example, and is not limited to this example.
  • the operation method of the fuel cell system according to the present embodiment includes a step in which the fuel cell generates power using the hydrogen-containing gas generated by the hydrogen-containing gas generation method according to any one of the first embodiment and Example 1-7. Prepare.
  • FIG. 3 is a diagram showing an example of a schematic configuration of a fuel cell system used in the operation method of the fuel cell system of the second embodiment.
  • the fuel cell system 200 includes a reformer 100 and a fuel cell 101.
  • the fuel cell 101 is a fuel cell that generates power using the hydrogen-containing gas supplied from the reformer 100.
  • the fuel cell 101 may be any type of fuel cell.
  • a polymer electrolyte fuel cell (PEFC) a solid oxide fuel cell, or a phosphoric acid fuel cell may be used.
  • the fuel cell system 200 During the power generation operation, the fuel cell system 200 generates power using the hydrogen-containing gas supplied from the reformer 100.
  • the power generation operation of the fuel cell 101 is known. Therefore, detailed description is omitted.
  • One embodiment of the present invention can generate a hydrogen-containing gas while suppressing the generation of ammonia as compared with the conventional one.

Abstract

This process for generating a hydrogen-containing gas is provided with a step of passing a raw material which is contaminated with molecular nitrogen and/or a nitrogen-containing compound through a first reforming catalyst (1) and a step of passing the resulting raw material through a second reforming catalyst (2) which is arranged on the downstream side of the first reforming catalyst (1) and which has a lower catalytic activity per unit quantity for reforming than that of the first reforming catalyst (1).

Description

水素含有ガスの生成方法および燃料電池システムの運転方法Method for producing hydrogen-containing gas and method for operating fuel cell system
　本発明は水素含有ガスの生成方法および燃料電池システムの運転方法に関する。 The present invention relates to a method for generating a hydrogen-containing gas and a method for operating a fuel cell system.
　従来より、改質反応を利用して原料から水素含有ガスを生成する方法がある。ここで、上記原料は、少なくとも炭素及び水素を構成元素とする有機化合物を含む。原料は、具体的には、原料ガスは、メタンを主成分とする都市ガス、天然ガス、ＬＰＧ等が例示される。 Conventionally, there is a method of generating a hydrogen-containing gas from a raw material using a reforming reaction. Here, the raw material contains at least an organic compound having carbon and hydrogen as constituent elements. Specifically, examples of the raw material gas include city gas mainly composed of methane, natural gas, and LPG.
　改質反応で生成された水素含有ガス中の一酸化炭素を低減するためのＣＯ低減器を設けても構わない。ＣＯ低減器は、シフト反応により一酸化炭素を低減させる変成器と、酸化反応及びメタン化反応の少なくともいずれか一方により一酸化炭素を低減させるＣＯ除去器との少なくともいずれか一方を備える。 A CO reducer for reducing carbon monoxide in the hydrogen-containing gas produced by the reforming reaction may be provided. The CO reducer includes at least one of a transformer that reduces carbon monoxide by a shift reaction and a CO remover that reduces carbon monoxide by at least one of an oxidation reaction and a methanation reaction.
　ここで、原料には、窒素分子、アミン等の窒素含有化合物が含まれると、改質反応により生成した水素と反応してアンモニアが生成され、このアンモニアが、ＣＯ除去器、燃料電池等の触媒毒になることが知られている（例えば、特許文献１参照）。 Here, when the raw material contains nitrogen-containing compounds such as nitrogen molecules and amines, it reacts with hydrogen produced by the reforming reaction to produce ammonia, which is used as a catalyst for CO removers, fuel cells, etc. It is known to become a poison (see, for example, Patent Document 1).
国際公開第２００７／０８１０１６号パンフレットInternational Publication No. 2007/081016 Pamphlet
　上記特許文献１記載の水素生成装置では、アンモニア被毒後に触媒を再生することについては検討されているが、アンモニアの生成を抑える水素含有ガスの生成方法については検討されていない。 In the hydrogen generator described in Patent Document 1, the regeneration of the catalyst after ammonia poisoning has been studied, but the method for producing a hydrogen-containing gas that suppresses the production of ammonia has not been studied.
　本発明は、上記従来の課題を解決するもので、従来よりもアンモニアの生成を抑える水素含有ガスの生成方法、及び燃料電池システムの運転方法を提供することを目的とする。 The present invention solves the above-described conventional problems, and an object of the present invention is to provide a method for producing a hydrogen-containing gas and a method for operating a fuel cell system, which suppress the production of ammonia as compared with the conventional art.
課題を解決する手段Means to solve the problem
　上記課題を解決するため、本発明の一態様の水素含有ガスの生成方法は、窒素分子及び窒素含有化合物の少なくともいずれか一方を含む原料を、第１の改質触媒を通過させるステップと、前記第１の改質触媒よりも下流に配設され、前記第１の改質触媒よりも改質反応に対する単位量当りの触媒能が低い第２の改質触媒を通過させるステップとを備える。 In order to solve the above problems, a method for producing a hydrogen-containing gas of one embodiment of the present invention includes a step of passing a raw material containing at least one of nitrogen molecules and a nitrogen-containing compound through a first reforming catalyst, And a step of passing a second reforming catalyst that is disposed downstream of the first reforming catalyst and has a lower catalytic ability per unit amount for the reforming reaction than the first reforming catalyst.
　本発明の一態様の水素含有ガスの生成方法によれば、従来よりもアンモニアの生成を抑えて水素含有ガスを生成し得る。 According to the method for producing a hydrogen-containing gas of one embodiment of the present invention, it is possible to produce a hydrogen-containing gas while suppressing the production of ammonia as compared with the conventional method.
図１は、実施の形態１の水素含有ガスの生成方法に用いる改質器の概略構成の一例を示す図である。FIG. 1 is a diagram illustrating an example of a schematic configuration of a reformer used in the method for generating a hydrogen-containing gas according to the first embodiment. 図２は、改質触媒の触媒能を比較した実験結果の一例を示す図である。FIG. 2 is a diagram showing an example of an experimental result comparing the catalytic ability of the reforming catalyst. 図３は、実施の形態２の燃料電池システムの運転方法に用いる燃料電池システムの概略構成の一例を示す図である。FIG. 3 is a diagram illustrating an example of a schematic configuration of a fuel cell system used in the operation method of the fuel cell system according to the second embodiment.
（実施の形態１）
　本発明者は、上記課題について鋭意検討した結果、以下の点に気付いた。 (Embodiment 1)
As a result of intensive studies on the above problems, the present inventor has noticed the following points.
　改質反応は吸熱反応であるため改質反応の反応量が相対的に少ない下流側の触媒は、上流側よりも相対的に温度が高くなる。温度が高くなると反応速度的にアンモニアの生成量が増加する。 Since the reforming reaction is an endothermic reaction, the downstream catalyst having a relatively small amount of reforming reaction has a relatively higher temperature than the upstream catalyst. As the temperature increases, the amount of ammonia produced increases in terms of reaction rate.
　そこで、本実施の形態の水素含有ガスの生成方法は、窒素分子及び窒素含有化合物の少なくともいずれか一方を含む原料を、第１の改質触媒を通過させるステップと、第１の改質触媒よりも下流に配設され、第１の改質触媒よりも改質反応に対する単位量当りの触媒能が低い第２の改質触媒を通過させるステップとを備える。 Therefore, in the method for generating a hydrogen-containing gas according to the present embodiment, the raw material containing at least one of nitrogen molecules and nitrogen-containing compounds is passed through the first reforming catalyst, and the first reforming catalyst is used. And a step of passing a second reforming catalyst which is disposed downstream and has a lower catalytic ability per unit amount for the reforming reaction than the first reforming catalyst.
　改質反応に対して単位量当りの触媒能が相対的に低い改質触媒では、アンモニアの生成の反応性も相対的に低くなることが知られている。 It is known that a reforming catalyst having a relatively low catalytic ability per unit amount with respect to the reforming reaction has a relatively low reactivity of ammonia generation.
　従って、上記水素含有ガスの生成方法により、第１の改質触媒よりも高温に維持される第２の改質触媒において、アンモニアの生成が抑制されるので、従来よりもアンモニアの生成を抑えて水素含有ガスを生成し得る。 Therefore, in the second reforming catalyst that is maintained at a higher temperature than the first reforming catalyst by the above-described method for producing the hydrogen-containing gas, the production of ammonia is suppressed. A hydrogen-containing gas can be produced.
　ここで、触媒能とは、改質反応を触媒する能力を意味する。 Here, the catalytic ability means the ability to catalyze the reforming reaction.
　図１は、実施の形態１の水素含有ガスの生成方法に用いる改質器の概略構成の一例を示す図である。 FIG. 1 is a diagram illustrating an example of a schematic configuration of a reformer used in the method for producing a hydrogen-containing gas according to the first embodiment.
　図１に示すように、改質器１００は、窒素分子及び窒素含有化合物の少なくともいずれか一方を含む原料を用いて水素含有ガスを生成する。 As shown in FIG. 1, the reformer 100 generates a hydrogen-containing gas using a raw material containing at least one of nitrogen molecules and nitrogen-containing compounds.
　具体的には、改質器１００内において、原料ガスが改質反応して、水素含有ガスが生成される。改質反応は、いずれの形態であってもよく、例えば、水蒸気改質反応、オートサーマル反応及び部分酸化反応等が挙げられる。図１には示されていないが、各改質反応において必要となる機器は適宜設けられる。例えば、改質反応が水蒸気改質反応であれば、改質器１００を加熱する燃焼器、水蒸気を生成する蒸発器、及び蒸発器に水を供給する水供給器が設けられる。改質反応がオートサーマル反応であれば、改質器１００には、さらに、改質器１００に空気を供給する空気供給器が設けられる。 Specifically, in the reformer 100, the raw material gas undergoes a reforming reaction to generate a hydrogen-containing gas. The reforming reaction may take any form, and examples thereof include a steam reforming reaction, an autothermal reaction, and a partial oxidation reaction. Although not shown in FIG. 1, equipment required for each reforming reaction is provided as appropriate. For example, if the reforming reaction is a steam reforming reaction, a combustor that heats the reformer 100, an evaporator that generates steam, and a water supplier that supplies water to the evaporator are provided. If the reforming reaction is an autothermal reaction, the reformer 100 is further provided with an air supply device that supplies air to the reformer 100.
　原料は、少なくとも炭素及び水素を構成元素とする有機化合物を含む。原料は、メタンを主成分とする都市ガス、天然ガス、ＬＰＧ等が例示される。窒素含有化合物は、アミン及びイソニトリル等が例示される。 The raw material contains at least an organic compound containing carbon and hydrogen as constituent elements. Examples of the raw material include city gas mainly composed of methane, natural gas, and LPG. Examples of the nitrogen-containing compound include amines and isonitriles.
　なお、改質器１００の下流に改質器１００で生成された水素含有ガス中の一酸化炭素を低減するためのＣＯ低減器を設けても構わない。ＣＯ低減器は、シフト反応により一酸化炭素を低減させる変成器と、酸化反応及びメタン化反応の少なくともいずれか一方により一酸化炭素を低減させるＣＯ除去器との少なくともいずれか一方を備える。 A CO reducer for reducing carbon monoxide in the hydrogen-containing gas produced by the reformer 100 may be provided downstream of the reformer 100. The CO reducer includes at least one of a transformer that reduces carbon monoxide by a shift reaction and a CO remover that reduces carbon monoxide by at least one of an oxidation reaction and a methanation reaction.
　図１に示すように、改質器１００は、第１の改質触媒１と、第１の改質触媒１の下流に配設された第２の改質触媒２とを備える。第１の改質触媒１および第２の改質触媒２はそれぞれ、触媒金属と触媒金属の担体とを備える。 As shown in FIG. 1, the reformer 100 includes a first reforming catalyst 1 and a second reforming catalyst 2 disposed downstream of the first reforming catalyst 1. Each of the first reforming catalyst 1 and the second reforming catalyst 2 includes a catalyst metal and a catalyst metal carrier.
　第２の改質触媒２は、第１の改質触媒１よりも改質反応に対する単位量当りの触媒能が低い。これを満たせば、第１の改質触媒１及び第２の改質触媒２は、いずれの形態であってもよいが、具体例については、以下の実施例で説明する。なお、単位量は、例えば、単位重量、単位体積、モル等が挙げられるが、これらに限定されるものではなく、一般的な単位量であればいずれの単位量であっても構わない。 The second reforming catalyst 2 has a lower catalytic ability per unit amount for the reforming reaction than the first reforming catalyst 1. If this is satisfied, the first reforming catalyst 1 and the second reforming catalyst 2 may be in any form, but specific examples will be described in the following examples. The unit amount includes, for example, a unit weight, a unit volume, and a mole, but is not limited to these, and any unit amount may be used as long as it is a general unit amount.
　上記改質器１００に、窒素分子及び窒素含有化合物の少なくともいずれか一方を含む原料が供給され、水素含有ガスが生成される。 A raw material containing at least one of nitrogen molecules and nitrogen-containing compounds is supplied to the reformer 100 to generate a hydrogen-containing gas.
　すなわち、本実施の形態の水素含有ガスの生成方法は、原料ガスを、相対的に改質反応に対する単位量当りの触媒能が高い第１の改質触媒１を通過させるステップと、第１の改質触媒１よりも下流に配設され、相対的に改質反応に対する単位量当りの触媒能が低い第２の改質触媒２を通過させるステップと、を備える。 That is, in the method for producing a hydrogen-containing gas according to the present embodiment, the step of passing the source gas through the first reforming catalyst 1 having a relatively high catalytic ability per unit amount for the reforming reaction, And a step of passing a second reforming catalyst 2 disposed downstream of the reforming catalyst 1 and having a relatively low catalytic ability per unit amount for the reforming reaction.
　ここで、上述の通り、改質触媒の改質反応は吸熱反応であるため、第１の改質触媒１よりも改質反応の反応量が少ない第２の改質触媒２は、第１の改質触媒１よりも温度が高くなりやすい。 Here, as described above, since the reforming reaction of the reforming catalyst is an endothermic reaction, the second reforming catalyst 2 having a smaller amount of reforming reaction than the first reforming catalyst 1 The temperature is likely to be higher than that of the reforming catalyst 1.
　また、図１に示すように、高温の燃焼排ガスにより第２の改質触媒２及び第１の改質触媒１の順に加熱されるよう構成されており、これによっても、第２の改質触媒２の方が、第１の改質触媒１よりも温度が高くなる。 Moreover, as shown in FIG. 1, it is comprised so that the 2nd reforming catalyst 2 and the 1st reforming catalyst 1 may be heated in order by the high-temperature combustion exhaust gas. 2 is higher in temperature than the first reforming catalyst 1.
　従って、第２の改質触媒２の方が、第１の改質触媒１よりも反応速度的にアンモニアの生成量が増加しやすくなる。 Therefore, the second reforming catalyst 2 is more likely to increase the amount of ammonia produced in terms of the reaction rate than the first reforming catalyst 1.
　しかしながら、上述の本実施の形態の水素含有ガスの生成方法を用いることで、上述の通り、従来よりもアンモニア生成量を抑制し得る。
［実施例１］
　実施例１では、第２の改質触媒の単位体積当たりの触媒金属の含有量が、第１の改質触媒のそれよりも少なくすることで、第２の改質触媒２は、第１の改質触媒１よりも改質反応に対する単位量当りの触媒能が低くなっている。 However, by using the method for producing a hydrogen-containing gas according to the present embodiment described above, as described above, the amount of ammonia produced can be suppressed more than before.
[Example 1]
In Example 1, the content of the catalyst metal per unit volume of the second reforming catalyst is less than that of the first reforming catalyst, so that the second reforming catalyst 2 The catalytic ability per unit amount for the reforming reaction is lower than that of the reforming catalyst 1.
　つまり、本実施例の水素含有ガスの生成方法は、窒素分子及び窒素含有化合物の少なくともいずれか一方を含む原料を、第１の改質触媒を通過させるステップと、第１の改質触媒よりも下流に配設され、単位体積当たりの触媒金属の含有量が、第１の改質触媒よりも少ない第２の改質触媒を通過させるステップとを備える。 That is, the method for generating a hydrogen-containing gas of the present embodiment includes a step of passing a raw material containing at least one of nitrogen molecules and a nitrogen-containing compound through the first reforming catalyst, and more than the first reforming catalyst. And passing a second reforming catalyst disposed downstream and having a catalytic metal content per unit volume less than that of the first reforming catalyst.
　実施例１の水素含有ガスの生成方法の具体例について、詳細に説明する。 Specific examples of the method for generating the hydrogen-containing gas of Example 1 will be described in detail.
　図２は、改質触媒の触媒能を比較した実験結果の一例を示す図である。 FIG. 2 is a diagram showing an example of an experimental result comparing the catalytic performance of the reforming catalyst.
　本実施例では、改質触媒が、Ｒｕを含有する触媒金属と、触媒金属の担体としてアルミナ担体とを備える。図２には、この改質触媒の単位体積あたりの触媒金属の含有量の違いによる改質反応に対する触媒能の相違を検討した実験結果が示されている。 In this embodiment, the reforming catalyst includes a catalyst metal containing Ru and an alumina support as a support for the catalyst metal. FIG. 2 shows the experimental results of examining the difference in catalytic ability for the reforming reaction due to the difference in the content of the catalytic metal per unit volume of the reforming catalyst.
　具体的には、アルミナ担体におけるＲｕの担持量が２ｗｔ％の改質触媒（以下、「２ｗｔ％Ｒｕ／アルミナ触媒」と略す場合がある）と、アルミナ担体におけるＲｕの担持量が０．５ｗｔ％の改質触媒（以下、「０．５ｗｔ％Ｒｕ／アルミナ触媒」と略す場合がある）とを準備した。これらの改質触媒について、図２に、改質触媒の温度（℃）と、改質触媒の触媒能を表すメタン（ＣＨ４）転化率（％）の関係が示されている。 Specifically, a reforming catalyst (hereinafter sometimes abbreviated as “2 wt% Ru / alumina catalyst”) having a Ru loading on the alumina support of 2 wt%, and a Ru loading on the alumina support of 0.5 wt%. The reforming catalyst (hereinafter sometimes abbreviated as “0.5 wt% Ru / alumina catalyst”) was prepared. For these reforming catalysts, FIG. 2 shows the relationship between the temperature (° C.) of the reforming catalyst and the methane (CH 4 ) conversion rate (%) representing the catalytic ability of the reforming catalyst.
　本実験では、固定床流通型反応装置に、２ｗｔ％Ｒｕ／アルミナ触媒および０．５ｗｔ％Ｒｕ／アルミナ触媒をそれぞれ、０．６ｃｃ充填させて、メタン流量が１００ｍｌ／ｍｉｎになるように、メタンが供給され、水流量が０．２０１ｇ／ｍｉｎとなるように、水が供給されている。この場合、ＳＶは１００００／ｈである。また、改質触媒の温度を調整するのに電気炉を用いて改質触媒が加熱され、改質触媒の出口ガスの濃度をガスクロマトグラフィーによって測定することによりメタン転化率が導かれている。 In this experiment, the fixed bed flow type reactor was filled with 0.6 cc of 2 wt% Ru / alumina catalyst and 0.5 wt% Ru / alumina catalyst, respectively, so that the methane flow rate was 100 ml / min. Water is supplied so that the water flow rate is 0.201 g / min. In this case, SV is 10,000 / h. Further, the reforming catalyst is heated using an electric furnace to adjust the temperature of the reforming catalyst, and the methane conversion rate is derived by measuring the concentration of the outlet gas of the reforming catalyst by gas chromatography.
　図２に示すように、約３５０℃～６５０℃の改質触媒の温度範囲において、２ｗｔ％Ｒｕ／アルミナ触媒が常に、０．５ｗｔ％Ｒｕ／アルミナ触媒よりもメタン転化率が大きい。つまり、単位体積当りの触媒金属の含有量が相対的に多い２ｗｔ％Ｒｕ／アルミナ触媒は、相対的に改質反応に対する単位量当りの触媒能が高い。一方、単位体積当りの触媒金属の含有量が相対的に少ない０．５ｗｔ％Ｒｕ／アルミナ触媒は、相対的に改質反応に対する単位量当りの触媒能が低い。 As shown in FIG. 2, in the temperature range of the reforming catalyst of about 350 ° C. to 650 ° C., the 2 wt% Ru / alumina catalyst always has a higher methane conversion rate than the 0.5 wt% Ru / alumina catalyst. That is, a 2 wt% Ru / alumina catalyst having a relatively high content of catalytic metal per unit volume has a relatively high catalytic ability per unit amount for the reforming reaction. On the other hand, a 0.5 wt% Ru / alumina catalyst having a relatively small content of catalytic metal per unit volume has a relatively low catalytic ability per unit amount for the reforming reaction.
　ところで、原料ガスの改質反応の進行において、第１の改質触媒１および第２の改質触媒２の触媒金属としてＲｕを用いる場合、第１の改質触媒１の温度は、例えば、４００℃程度、第２の改質触媒２の温度は、例えば、６００℃程度に調整される。 By the way, when Ru is used as the catalyst metal of the first reforming catalyst 1 and the second reforming catalyst 2 in the progress of the reforming reaction of the raw material gas, the temperature of the first reforming catalyst 1 is, for example, 400 For example, the temperature of the second reforming catalyst 2 is adjusted to about 600 ° C.
　この場合、原料ガスに、窒素分子及び窒素含有化合物の少なくともいずれか一方が含まれると、原料ガスの改質反応の進行とともに、アンモニアが生成し、アンモニア生成量は改質触媒の温度に大きく依存する。例えば、窒素を２％程度含む原料ガスの改質反応の進行の場合、２ｗｔ％Ｒｕ／アルミナ触媒では、改質触媒の温度が４００℃の条件下において、アンモニアの生成量は１ｐｐｍ以下であるが、６００℃では、１０ｐｐｍ程度となる。一方、０．５ｗｔ％Ｒｕ／アルミナ触媒では、アンモニア生成量を、６００℃でも１ｐｐｍ程度に抑制できる。このため、相対的に改質反応に対する単位量当りの触媒能が高い２ｗｔ％Ｒｕ／アルミナ触媒は、アンモニアを生成反応を触媒する能力も高いので、アンモニア生成量を抑制するには、かかる改質触媒を低温で使用することが好ましい。一方、相対的に改質反応に対する単位量当りの触媒能が低い０．５ｗｔ％Ｒｕ／アルミナ触媒は、高温でもアンモニア生成量を抑制し得る。 In this case, if the source gas contains at least one of nitrogen molecules and nitrogen-containing compounds, ammonia is generated as the reforming reaction of the source gas proceeds, and the amount of ammonia generated greatly depends on the temperature of the reforming catalyst. To do. For example, in the case of a reforming reaction of a raw material gas containing about 2% nitrogen, a 2 wt% Ru / alumina catalyst has an ammonia production amount of 1 ppm or less under the condition that the temperature of the reforming catalyst is 400 ° C. At 600 ° C., it becomes about 10 ppm. On the other hand, with the 0.5 wt% Ru / alumina catalyst, the amount of ammonia produced can be suppressed to about 1 ppm even at 600 ° C. For this reason, the 2 wt% Ru / alumina catalyst, which has a relatively high catalytic capacity per unit amount for the reforming reaction, has a high ability to catalyze the reaction for generating ammonia. It is preferred to use the catalyst at a low temperature. On the other hand, a 0.5 wt% Ru / alumina catalyst having a relatively low catalytic ability per unit amount for the reforming reaction can suppress an ammonia production amount even at a high temperature.
　そこで、本実施例の改質器１００では、第１の改質触媒１に２ｗｔ％Ｒｕ／アルミナ触媒を用い、第２の改質触媒２に０．５ｗｔ％Ｒｕ／アルミナ触媒を用いる。
よって、本実施例の水素含有ガスの生成方法は、従来よりもアンモニアの生成を抑えて水素含有ガスを生成し得る。 Therefore, in the reformer 100 of this embodiment, a 2 wt% Ru / alumina catalyst is used for the first reforming catalyst 1 and a 0.5 wt% Ru / alumina catalyst is used for the second reforming catalyst 2.
Therefore, the method for producing the hydrogen-containing gas of the present embodiment can produce the hydrogen-containing gas while suppressing the production of ammonia as compared with the conventional method.
　なお、第１の改質触媒１および第２の改質触媒２の触媒金属としての上記のＲｕは、例示であって、第１の改質触媒１および第２の改質触媒２の触媒金属は、改質反応を進行させることが可能な触媒金属であれば、いずれであっても構わず、本例に限定されるものではない。なお、第１の改質触媒１および第２の改質触媒２の触媒金属は、一般的に、Ｐｔ、Ｒｕ、Ｒｈ、Ｐｄ等の貴金属系触媒及びＮｉ系からなる群の中から選択される少なくとも１種を好適に用いることができる。 Note that the above Ru as the catalyst metal of the first reforming catalyst 1 and the second reforming catalyst 2 is an example, and the catalyst metal of the first reforming catalyst 1 and the second reforming catalyst 2 is an example. Any catalyst metal can be used as long as it can cause the reforming reaction to proceed, and the present invention is not limited to this example. The catalyst metals of the first reforming catalyst 1 and the second reforming catalyst 2 are generally selected from the group consisting of noble metal catalysts such as Pt, Ru, Rh, Pd, and Ni-based catalysts. At least one kind can be suitably used.
　また、第１の改質触媒１および第２の改質触媒２の触媒金属は、同一金属種でも異なる金属種でもよい。なお、第１の改質触媒１および第２の改質触媒２の触媒金属が、異なる金属種であるときは、第２の触媒金属は、改質反応に対する触媒能が第１の触媒金属以下となる。 Further, the catalyst metal of the first reforming catalyst 1 and the second reforming catalyst 2 may be the same metal species or different metal species. In addition, when the catalytic metals of the first reforming catalyst 1 and the second reforming catalyst 2 are different metal species, the second catalytic metal has a catalytic ability for the reforming reaction equal to or lower than that of the first catalytic metal. It becomes.
　また、第１の改質触媒１および第２の改質触媒２の担体としての上記のアルミナ担体は、例示であって、第１の改質触媒１および第２の改質触媒２の担体は、本例に限定されるものではない。第１の改質触媒１および第２の改質触媒２の触媒金属の担体は、触媒金属を担持可能なものであれば、どのような担体でもよい。 The above-mentioned alumina carrier as the carrier of the first reforming catalyst 1 and the second reforming catalyst 2 is an example, and the carrier of the first reforming catalyst 1 and the second reforming catalyst 2 is However, the present invention is not limited to this example. The catalyst metal carrier of the first reforming catalyst 1 and the second reforming catalyst 2 may be any carrier as long as it can carry the catalyst metal.
　また、第１の改質触媒１および第２の改質触媒２の上記のＲｕの担持量は、例示であって、第１の改質触媒１および第２の改質触媒２の単位体積当たりの触媒金属の含有量は、本例に限定されるものではない。 Further, the above-mentioned Ru loadings of the first reforming catalyst 1 and the second reforming catalyst 2 are examples, and per unit volume of the first reforming catalyst 1 and the second reforming catalyst 2. The content of the catalyst metal is not limited to this example.
　また、第１の改質触媒１および第２の改質触媒２の上記の温度およびＳＶは、例示であって、これらは、本例に限定されるものではない。 Further, the above temperature and SV of the first reforming catalyst 1 and the second reforming catalyst 2 are merely examples, and these are not limited to this example.
　なお、本実施例では、改質触媒に対するアンモニア生成を抑制する効果以外にも、以下の効果がある。 In this embodiment, in addition to the effect of suppressing ammonia generation for the reforming catalyst, there are the following effects.
　Ｒｕ系の改質触媒は一般的に硫黄被毒されるため、原料ガス中に硫黄を含む場合は、吸着脱硫剤または水添脱硫剤を改質触媒の前段に設けて、硫黄を除去している。しかし、硫黄を完全に除去することは困難であり、数ｐｐｂ程度は改質触媒へ供給されてしまう場合がある。そこで、上記のとおり、第１の改質触媒１に、相対的に改質反応に対する触媒能が高い触媒を充填すると、硫黄が供給されても改質反応の性能が低下しにくいので、改質触媒の耐久性において有利である。また、硫黄は第１の改質触媒１でトラップされるので、第２の改質触媒２が、相対的に改質反応に対する触媒能が低い触媒があっても、硫黄による改質反応の性能低下を抑制できる。
［実施例２］
　実施例２では、第２の改質触媒の比表面積は、第１の改質触媒のそれよりも小さくすることで、第２の改質触媒２は、第１の改質触媒１よりも改質反応に対する単位量当りの触媒能が低くなっている。 Since Ru-based reforming catalysts are generally poisoned with sulfur, if the source gas contains sulfur, an adsorptive desulfurizing agent or hydrodesulfurizing agent is provided in the front stage of the reforming catalyst to remove sulfur. Yes. However, it is difficult to completely remove sulfur, and about several ppb may be supplied to the reforming catalyst. Therefore, as described above, when the first reforming catalyst 1 is filled with a catalyst having a relatively high catalytic capacity for the reforming reaction, the performance of the reforming reaction is hardly lowered even if sulfur is supplied. This is advantageous in terms of catalyst durability. In addition, since sulfur is trapped by the first reforming catalyst 1, even if the second reforming catalyst 2 has a catalyst having a relatively low catalytic ability for the reforming reaction, the performance of the reforming reaction by sulfur. Reduction can be suppressed.
[Example 2]
In Example 2, the specific surface area of the second reforming catalyst is made smaller than that of the first reforming catalyst, so that the second reforming catalyst 2 is modified more than the first reforming catalyst 1. The catalytic ability per unit amount for the quality reaction is low.
　つまり、本実施例の水素含有ガスの生成方法は、窒素分子及び窒素含有化合物の少なくともいずれか一方を含む原料を、第１の改質触媒を通過させるステップと、第１の改質触媒よりも下流に配設され、比表面積が第１の改質触媒よりも小さい第２の改質触媒を通過させるステップとを備える。　実施例２の水素含有ガスの生成方法の具体例について、詳細に説明する。 That is, the method for generating a hydrogen-containing gas of the present embodiment includes a step of passing a raw material containing at least one of nitrogen molecules and a nitrogen-containing compound through the first reforming catalyst, and more than the first reforming catalyst. And passing a second reforming catalyst disposed downstream and having a specific surface area smaller than that of the first reforming catalyst. A specific example of the method for generating the hydrogen-containing gas of Example 2 will be described in detail.
　本実施例も、実施例１と同様に、第１の改質触媒及び第２改質触媒は、共にＲｕを含有する触媒金属と、触媒金属の担体としてアルミナ担体とを備え、第２の改質触媒が第１の改質触媒の下流に配設されている。 In this example, as in Example 1, both the first reforming catalyst and the second reforming catalyst include a catalyst metal containing Ru and an alumina support as a catalyst metal support. A quality catalyst is disposed downstream of the first reforming catalyst.
　そして、第２の改質触媒の比表面積は、第１の改質触媒の比表面積よりも小さい。 The specific surface area of the second reforming catalyst is smaller than the specific surface area of the first reforming catalyst.
　一般的に、比表面積が大きい改質触媒の方が、改質反応に対する触媒能が高い。 Generally, a reforming catalyst having a large specific surface area has a higher catalytic ability for the reforming reaction.
　よって、第１の改質触媒１よりも比表面積の小さい第２の改質触媒２は、第１の改質触媒１よりも、相対的に改質反応に対する単位量当りの触媒能が低くなる。 Therefore, the second reforming catalyst 2 having a specific surface area smaller than that of the first reforming catalyst 1 is relatively lower in catalytic ability per unit amount for the reforming reaction than the first reforming catalyst 1. .
　本実施例では、上記第１の改質触媒１及び第２の改質触媒２を備える改質器に窒素分子及び窒素含有化合物の少なくともいずれか一方を含む原料を通過させ、改質反応を進行させ、水素含有ガスを生成する。 In this embodiment, a raw material containing at least one of nitrogen molecules and a nitrogen-containing compound is passed through a reformer including the first reforming catalyst 1 and the second reforming catalyst 2 to advance the reforming reaction. To produce a hydrogen-containing gas.
　よって、本実施例の水素含有ガスの生成方法は、従来よりもアンモニアの生成を抑えて水素含有ガスを生成し得る。　なお、第１の改質触媒１および第２の改質触媒２の触媒金属としての上記のＲｕは、例示であって、第１の改質触媒１および第２の改質触媒２の触媒金属は、改質反応を進行させることが可能な触媒金属であれば、いずれであっても構わず、本例に限定されるものではない。なお、第１の改質触媒１および第２の改質触媒２の触媒金属は、一般的に、Ｐｔ、Ｒｕ、Ｒｈ、Ｐｄ等の貴金属系触媒及びＮｉ系からなる群の中から選択される少なくとも１種を好適に用いることができる。 Therefore, the method for producing a hydrogen-containing gas according to the present embodiment can produce a hydrogen-containing gas while suppressing the production of ammonia as compared with the conventional method. Note that the above Ru as the catalyst metal of the first reforming catalyst 1 and the second reforming catalyst 2 is an example, and the catalyst metal of the first reforming catalyst 1 and the second reforming catalyst 2 is an example. Any catalyst metal can be used as long as it can cause the reforming reaction to proceed, and the present invention is not limited to this example. The catalyst metals of the first reforming catalyst 1 and the second reforming catalyst 2 are generally selected from the group consisting of noble metal catalysts such as Pt, Ru, Rh, Pd, and Ni-based catalysts. At least one kind can be suitably used.
　また、第１の改質触媒１および第２の改質触媒２の触媒金属は、同一金属種でも異なる金属種でもよい。なお、第１の改質触媒１および第２の改質触媒２の触媒金属が、異なる金属種であるときは、第２の触媒金属は、改質反応に対する触媒能が第１の触媒金属以下となる。 Further, the catalyst metal of the first reforming catalyst 1 and the second reforming catalyst 2 may be the same metal species or different metal species. In addition, when the catalytic metals of the first reforming catalyst 1 and the second reforming catalyst 2 are different metal species, the second catalytic metal has a catalytic ability for the reforming reaction equal to or lower than that of the first catalytic metal. It becomes.
　また、第１の改質触媒１および第２の改質触媒２の担体としての上記のアルミナ担体は、例示であって、第１の改質触媒１および第２の改質触媒２の担体は、本例に限定されるものではない。第１の改質触媒１および第２の改質触媒２の触媒金属の担体は、触媒金属を担持可能なものであれば、どのような担体でもよい。
［実施例３］
　実施例３では、第２の改質触媒に含まれる触媒金属を担持する第２の担体は、第１の改質触媒に含まれる触媒金属を担持する第１の担体よりも改質反応に対する担体効果が低くなっている。これにより、第２の改質触媒２は、第１の改質触媒１よりも改質反応に対する単位量当りの触媒能が低くなっている。 The above-mentioned alumina carrier as the carrier of the first reforming catalyst 1 and the second reforming catalyst 2 is an example, and the carrier of the first reforming catalyst 1 and the second reforming catalyst 2 is However, the present invention is not limited to this example. The catalyst metal carrier of the first reforming catalyst 1 and the second reforming catalyst 2 may be any carrier as long as it can carry the catalyst metal.
[Example 3]
In Example 3, the second carrier carrying the catalyst metal contained in the second reforming catalyst is more suitable for the reforming reaction than the first carrier carrying the catalyst metal contained in the first reforming catalyst. The effect is low. As a result, the second reforming catalyst 2 has a lower catalytic ability per unit amount for the reforming reaction than the first reforming catalyst 1.
　つまり、本実施例の水素含有ガスの生成方法は、窒素分子及び窒素含有化合物の少なくともいずれか一方を含む原料を、第１の改質触媒を通過させるステップと、第１の改質触媒よりも下流に配設され、担体効果が第１の改質触媒よりも小さい第２の改質触媒を通過させるステップとを備える。 That is, the method for generating a hydrogen-containing gas of the present embodiment includes a step of passing a raw material containing at least one of nitrogen molecules and a nitrogen-containing compound through the first reforming catalyst, and more than the first reforming catalyst. And passing a second reforming catalyst disposed downstream and having a carrier effect smaller than that of the first reforming catalyst.
　なお、第１の改質触媒と第２の改質触媒とが、同一の触媒金属を備えている。 Note that the first reforming catalyst and the second reforming catalyst are provided with the same catalyst metal.
　実施例３の水素含有ガスの生成方法の具体例について、詳細に説明する。 Specific examples of the method for generating the hydrogen-containing gas of Example 3 will be described in detail.
　本実施例も、実施例１及び実施例２と同様に、第１の改質触媒及び第２改質触媒は、共にＲｕを含有する触媒金属を備える。 In the present example, as in Example 1 and Example 2, both the first reforming catalyst and the second reforming catalyst include a catalyst metal containing Ru.
　ただし、実施例１及び実施例２と異なり本実施例では、第１の改質触媒が備える触媒金属を担持する第１の担体と、第２の改質触媒が備える触媒金属を担持する第２の担体とは異なる。 However, unlike Example 1 and Example 2, in this example, the first carrier supporting the catalyst metal included in the first reforming catalyst and the second carrier supporting the catalyst metal included in the second reforming catalyst. Different from the carrier.
　具体的には、第２の担体が、第１の担体よりも改質反応に対する担体効果が低い。 Specifically, the second carrier has a lower carrier effect on the reforming reaction than the first carrier.
　例えば、アルミナ担体よりもジルコニア担体を用いる方が、改質反応に対する担体効果が低くなる。そこで、本実施例では、第１の改質触媒１には担体効果が高いアルミナ担体を用い、第２の改質触媒２には担体効果が低いジルコニア担体を用いている。 For example, the use of a zirconia support rather than an alumina support has a lower support effect on the reforming reaction. Therefore, in this embodiment, an alumina carrier having a high carrier effect is used for the first reforming catalyst 1, and a zirconia carrier having a low carrier effect is used for the second reforming catalyst 2.
　よって、第１の担体よりも担体効果の小さい第２の担体を備える第２の改質触媒は、第１の改質触媒よりも相対的に改質反応に対する単位量当りの触媒能が低くなる。 Therefore, the second reforming catalyst including the second carrier having a smaller carrier effect than the first carrier has a lower catalytic ability per unit amount relative to the reforming reaction than the first reforming catalyst. .
　そして、本実施例では、上記第１の担体及び第２の担体を備える第１の改質触媒１及び第２の改質触媒２に、窒素分子及び窒素含有化合物の少なくともいずれか一方を含む原料を通過させ、改質反応を進行させ、水素含有ガスを生成する。 In this embodiment, the first reforming catalyst 1 and the second reforming catalyst 2 each including the first carrier and the second carrier include a raw material containing at least one of a nitrogen molecule and a nitrogen-containing compound. And a reforming reaction proceeds to produce a hydrogen-containing gas.
　よって、本実施例の水素含有ガスの生成方法は、従来よりもアンモニアの生成を抑えて水素含有ガスを生成し得る。 Therefore, the method for producing a hydrogen-containing gas according to the present embodiment can produce a hydrogen-containing gas while suppressing the production of ammonia as compared with the conventional method.
　なお、第１の改質触媒１および第２の改質触媒２の触媒金属としての上記のＲｕは、例示であって、第１の改質触媒１および第２の改質触媒２の触媒金属は、改質反応を進行させることが可能な触媒金属であれば、いずれであっても構わず、本例に限定されるものではない。第１の改質触媒１および第２の改質触媒２の触媒金属は、一般的に、Ｐｔ、Ｒｕ、Ｒｈ、Ｐｄ等の貴金属系触媒及びＮｉ系からなる群の中から選択される少なくとも１種を好適に用いることができる。 Note that the above Ru as the catalyst metal of the first reforming catalyst 1 and the second reforming catalyst 2 is an example, and the catalyst metal of the first reforming catalyst 1 and the second reforming catalyst 2 is an example. Any catalyst metal can be used as long as it can cause the reforming reaction to proceed, and the present invention is not limited to this example. The catalyst metal of the first reforming catalyst 1 and the second reforming catalyst 2 is generally at least one selected from the group consisting of noble metal catalysts such as Pt, Ru, Rh, Pd, and Ni-based catalysts. Species can be suitably used.
　また、第１の改質触媒１および第２の改質触媒２の触媒金属は、同一金属種でも異なる金属種でもよい。なお、第１の改質触媒１および第２の改質触媒２の触媒金属が、異なる金属種であるときは、第２の触媒金属は、改質反応に対する触媒能が第１の触媒金属以下となる。 Further, the catalyst metal of the first reforming catalyst 1 and the second reforming catalyst 2 may be the same metal species or different metal species. In addition, when the catalytic metals of the first reforming catalyst 1 and the second reforming catalyst 2 are different metal species, the second catalytic metal has a catalytic ability for the reforming reaction equal to or lower than that of the first catalytic metal. It becomes.
　また、第１の改質触媒１および第２の改質触媒２の担体としての上記のアルミナ担体およびジルコニア担体は、例示であって、第１の改質触媒１および第２の改質触媒２の担体は、本例に限定されるものではない。第１の改質触媒１および第２の改質触媒２の触媒金属の担体は、上記の担体効果の高低関係を満たして、触媒金属を担持可能なものであれば、どのような担体でもよい。
［実施例４］
　実施例４では、第１の改質触媒と第２の改質触媒とが、触媒金属としてＮｉを含有する触媒である。 Further, the above-described alumina carrier and zirconia carrier as carriers for the first reforming catalyst 1 and the second reforming catalyst 2 are examples, and the first reforming catalyst 1 and the second reforming catalyst 2 are examples. The carrier is not limited to this example. The carrier of the catalyst metal of the first reforming catalyst 1 and the second reforming catalyst 2 may be any carrier as long as it satisfies the above-described level of the carrier effect and can carry the catalyst metal. .
[Example 4]
In Example 4, the first reforming catalyst and the second reforming catalyst are catalysts containing Ni as a catalyst metal.
　また、本実施例では、実施例１と同様に、第２の改質触媒の単位体積当たりの触媒金属の含有量が、第１の改質触媒１のそれよりも少なくすることで、第２の改質触媒２は、第１の改質触媒１よりも改質反応に対する単位量当りの触媒能が低くなっている。 In the present embodiment, as in the first embodiment, the content of the catalyst metal per unit volume of the second reforming catalyst is less than that of the first reforming catalyst 1, so that the second The reforming catalyst 2 has a lower catalytic ability per unit amount for the reforming reaction than the first reforming catalyst 1.
　実施例４の水素含有ガスの生成方法の具体例について、詳細に説明する。 Specific examples of the method for generating the hydrogen-containing gas of Example 4 will be described in detail.
　本実施例では、第１の改質触媒と第２の改質触媒とが、共にＮｉを含有する触媒金属と、触媒金属の担体としてアルミナ担体とを備え、第２の改質触媒が第１の改質触媒の下流に配設されている。 In the present embodiment, the first reforming catalyst and the second reforming catalyst both include a catalyst metal containing Ni and an alumina carrier as a carrier for the catalyst metal, and the second reforming catalyst is the first reforming catalyst. Is disposed downstream of the reforming catalyst.
　本例では、第１の改質触媒が、第２の改質触媒よりも単位体積当りの触媒金属の含有量が相対的に多くなるよう構成されている。 In this example, the first reforming catalyst is configured so that the content of the catalytic metal per unit volume is relatively larger than that of the second reforming catalyst.
　具体的には、本実施例では、第１の改質触媒１として、アルミナ担体におけるＮｉを含有する触媒金属の担持量が３０ｗｔ％の改質触媒を用い、第２の改質触媒２として、アルミナ担体におけるＮｉを含有する触媒金属の担持量が２０ｗｔ％の改質触媒を用いている。 Specifically, in the present embodiment, as the first reforming catalyst 1, a reforming catalyst having a supported amount of catalytic metal containing Ni in an alumina carrier of 30 wt% is used, and as the second reforming catalyst 2, A reforming catalyst in which the supported amount of the catalyst metal containing Ni on the alumina support is 20 wt% is used.
　そして、実施例１と同様に、単位体積当りのＮｉを含有する触媒金属の含有量が多い改質触媒の方が、メタン転化率が高い。つまり、改質反応に対する触媒能が高い。 And, as in Example 1, the reforming catalyst having a higher content of catalytic metal containing Ni per unit volume has a higher methane conversion rate. That is, the catalytic ability for the reforming reaction is high.
　よって、第１の改質触媒１よりも単位体積当りの触媒金属の含有量の少ない第２の改質触媒２は、相対的に改質反応に対する単位量当りの触媒能が低くなる。 Therefore, the second reforming catalyst 2 having a lower catalyst metal content per unit volume than the first reforming catalyst 1 has a relatively low catalytic ability per unit amount for the reforming reaction.
　よって、本実施例の水素含有ガスの生成方法は、従来よりもアンモニアの生成を抑えて水素含有ガスを生成し得る。 Therefore, the method for producing a hydrogen-containing gas according to the present embodiment can produce a hydrogen-containing gas while suppressing the production of ammonia as compared with the conventional method.
　また、第１の改質触媒１および第２の改質触媒２の担体としての上記のアルミナ担体は、例示であって、第１の改質触媒１および第２の改質触媒２の担体は、本例に限定されるものではない。第１の改質触媒１および第２の改質触媒２の触媒金属の担体は、触媒金属を担持可能なものであれば、どのような担体でもよい。 The above-mentioned alumina carrier as the carrier of the first reforming catalyst 1 and the second reforming catalyst 2 is an example, and the carrier of the first reforming catalyst 1 and the second reforming catalyst 2 is However, the present invention is not limited to this example. The catalyst metal carrier of the first reforming catalyst 1 and the second reforming catalyst 2 may be any carrier as long as it can carry the catalyst metal.
　また、第１の改質触媒１および第２の改質触媒２の上記のＮｉの担持量は、例示であって、第１の改質触媒１および第２の改質触媒２の単位体積当たりの触媒金属の含有量は、本例に限定されるものではない。 Further, the above-mentioned amount of Ni supported by the first reforming catalyst 1 and the second reforming catalyst 2 is an exemplification, and per unit volume of the first reforming catalyst 1 and the second reforming catalyst 2. The content of the catalyst metal is not limited to this example.
　なお、本実施例では、実施例１と同様に、第２の改質触媒の単位体積当たりの触媒金属の含有量が、第１の改質触媒１のそれよりも少なくすることで、第２の改質触媒２は、第１の改質触媒１よりも改質反応に対する単位量当りの触媒能が低くしているが、これに限定されない。 In the present embodiment, as in the first embodiment, the content of the catalyst metal per unit volume of the second reforming catalyst is less than that of the first reforming catalyst 1, so that the second The reforming catalyst 2 has lower catalytic ability per unit amount for the reforming reaction than the first reforming catalyst 1, but is not limited thereto.
　第２の改質触媒２の改質反応に対する単位量当りの触媒能を、第１の改質触媒１のそれよりも低くするために、実施例２または実施例３のような方法を採用しても構わない。
［実施例５］
　実施例５の水素含有ガスの生成方法について説明する。 In order to make the catalytic performance per unit amount for the reforming reaction of the second reforming catalyst 2 lower than that of the first reforming catalyst 1, a method like Example 2 or Example 3 is adopted. It doesn't matter.
[Example 5]
A method for producing the hydrogen-containing gas of Example 5 will be described.
　本実施例の水素含有ガスの生成方法は、第１の改質触媒と第２の改質触媒とが分割されていている。 In the method for generating a hydrogen-containing gas according to this embodiment, the first reforming catalyst and the second reforming catalyst are divided.
　第１の改質触媒１と第２の改質触媒２とが分割された配置を取ると、改質器１００の上流側に第１の改質触媒１を充填できる。また、改質器１００の下流側に第２の改質触媒２を充填できる。なお、この場合、第１の改質触媒１と第２の改質触媒２とを仕切る仕切部材（図示せず）を設けてもよい。仕切部材には、ガスを通して改質触媒を通さない複数の孔を形成してもよい。 If the first reforming catalyst 1 and the second reforming catalyst 2 are divided, the first reforming catalyst 1 can be filled upstream of the reformer 100. Further, the second reforming catalyst 2 can be filled on the downstream side of the reformer 100. In this case, a partition member (not shown) for partitioning the first reforming catalyst 1 and the second reforming catalyst 2 may be provided. A plurality of holes that do not allow the reforming catalyst to pass through the gas may be formed in the partition member.
　なお、第１の改質触媒１および第２の改質触媒２の上記の分割配置は、例示であって、第１の改質触媒１および第２の改質触媒２の配置の形態は、本例に限定されるものではない。第１の改質触媒１および第２の改質触媒２の間で上記の触媒能の高低関係を満たせば、第１の改質触媒１および第２の改質触媒２をどのように配置してもよい。 The above-described divided arrangement of the first reforming catalyst 1 and the second reforming catalyst 2 is an example, and the form of arrangement of the first reforming catalyst 1 and the second reforming catalyst 2 is as follows. It is not limited to this example. If the above-described high / low relation of the catalytic ability is satisfied between the first reforming catalyst 1 and the second reforming catalyst 2, how the first reforming catalyst 1 and the second reforming catalyst 2 are arranged. May be.
　例えば、改質器１００の少なくとも一部において、第１の改質触媒１及び第２の改質触媒２と、が混合されており、下流に向かうに従って第１の改質触媒の濃度が低くなるよう、濃度勾配を持たせる配置の形態であってもよい。
［実施例６］
　実施例６では、実施例１－実施例５の水素含有ガスの生成方法において、第２の改質触媒は、第１の改質触媒よりも触媒量を多くしている。 For example, in at least a part of the reformer 100, the first reforming catalyst 1 and the second reforming catalyst 2 are mixed, and the concentration of the first reforming catalyst decreases toward the downstream. As such, it may be in the form of an arrangement having a concentration gradient.
[Example 6]
In Example 6, in the method for producing the hydrogen-containing gas of Example 1 to Example 5, the amount of the second reforming catalyst is larger than that of the first reforming catalyst.
　つまり、本実施例の水素含有ガスの生成方法は、窒素分子及び窒素含有化合物の少なくともいずれか一方を含む原料を、第１の改質触媒を通過させるステップと、第１の改質触媒よりも下流に配設され、改質反応に対する触媒能が第１の改質触媒よりも小さい第２の改質触媒を通過させるステップとを備え、第２の改質触媒は、第１の改質触媒よりも触媒量が多い。 That is, the method for generating a hydrogen-containing gas of the present embodiment includes a step of passing a raw material containing at least one of nitrogen molecules and a nitrogen-containing compound through the first reforming catalyst, and more than the first reforming catalyst. A second reforming catalyst disposed downstream and passing a second reforming catalyst having a catalytic capacity for the reforming reaction that is smaller than that of the first reforming catalyst, wherein the second reforming catalyst is a first reforming catalyst. More catalyst than
　実施例６の水素含有ガスの生成方法の具体例について、詳細に説明する。 A specific example of the method for generating the hydrogen-containing gas of Example 6 will be described in detail.
　本実施例では、改質器１００に設けられた第１の改質触媒１及び第２の改質触媒２は、実施例１－５のいずれかの方法により、第２の改質触媒２は、第１の改質触媒１よりも改質反応に対する単位量当りの触媒能が低くなっている。 In this embodiment, the first reforming catalyst 1 and the second reforming catalyst 2 provided in the reformer 100 are converted into the second reforming catalyst 2 by any one of the methods in Embodiment 1-5. The catalytic performance per unit amount for the reforming reaction is lower than that of the first reforming catalyst 1.
　さらに、第２の改質触媒は、第１の改質触媒よりも触媒量が多い。 Furthermore, the second reforming catalyst has a larger amount of catalyst than the first reforming catalyst.
　第２の改質触媒２は、相対的に改質反応に対する単位量当りの触媒能が低いので、メタン転化率が平衡を下回りやすいが、第２の改質触媒２の触媒量を増やし、ＳＶを低下させることでメタン転化率が平衡に近づくので好ましい。 Since the second reforming catalyst 2 has a relatively low catalytic capacity per unit amount for the reforming reaction, the methane conversion rate tends to be lower than the equilibrium, but the amount of the second reforming catalyst 2 is increased to increase SV. Is preferable because the methane conversion rate approaches equilibrium.
　また、第１の改質触媒１の触媒量を増やすと、第１の改質触媒１が、改質器１００の下流側の高温領域に近い位置まで充填される場合がある。この場合、第１の改質触媒１が、高温状態で使用される可能性が生じ、第１の改質触媒１において、アンモニアを生成しやすくなる。 Further, when the catalyst amount of the first reforming catalyst 1 is increased, the first reforming catalyst 1 may be charged to a position close to the high temperature region on the downstream side of the reformer 100. In this case, there is a possibility that the first reforming catalyst 1 is used in a high temperature state, and ammonia is easily generated in the first reforming catalyst 1.
　このため、第２の改質触媒２は、第１の改質触媒１よりも触媒量を多くする方が好ましい。 Therefore, it is preferable that the second reforming catalyst 2 has a larger amount of catalyst than the first reforming catalyst 1.
　第１の改質触媒１の触媒量と第２の改質触媒２の触媒量との比率が、例えば、１：２となるように、第１の改質触媒１および第２の改質触媒２を改質器１００に充填してもよいし、また、第２の改質触媒２の触媒量を更に増やしてもよい。但し、改質器の低コスト化、および、コンパクト化の点から考慮すると、上記の比率は、１：２から１：５程度にする方が好ましい。
［実施例７］
　実施例７では、第２の改質触媒が備える触媒金属の改質反応に対する触媒能を、第１の改質触媒が備える触媒金属のそれよりも低くすることで、第２の改質触媒２は、第１の改質触媒１よりも改質反応に対する単位量当りの触媒能が低くなっている。 The first reforming catalyst 1 and the second reforming catalyst are set so that the ratio between the catalyst amount of the first reforming catalyst 1 and the catalyst amount of the second reforming catalyst 2 is, for example, 1: 2. 2 may be charged into the reformer 100, or the amount of the second reforming catalyst 2 may be further increased. However, considering the cost reduction and compactness of the reformer, the above ratio is preferably about 1: 2 to 1: 5.
[Example 7]
In Example 7, the catalytic capacity for the reforming reaction of the catalyst metal included in the second reforming catalyst is made lower than that of the catalyst metal included in the first reforming catalyst, whereby the second reforming catalyst 2 Is lower in catalytic ability per unit amount than the first reforming catalyst 1 for the reforming reaction.
　つまり、本実施例の水素含有ガスの生成方法は、窒素分子及び窒素含有化合物の少なくともいずれか一方を含む原料を、第１の改質触媒を通過させるステップと、第１の改質触媒よりも下流に配設され、触媒金属の改質反応に対する触媒能が第１の改質触媒よりも低い第２の改質触媒を通過させるステップとを備える。
実施例７の水素含有ガスの生成方法の具体例について、詳細に説明する。 That is, the method for generating a hydrogen-containing gas of the present embodiment includes a step of passing a raw material containing at least one of nitrogen molecules and a nitrogen-containing compound through the first reforming catalyst, and more than the first reforming catalyst. And a step of passing a second reforming catalyst disposed downstream and having a catalytic ability for the reforming reaction of the catalytic metal lower than that of the first reforming catalyst.
A specific example of the method for generating the hydrogen-containing gas of Example 7 will be described in detail.
　改質触媒は、同一の使用条件においては、Ｒｕ触媒、Ｒｕ－Ｐｔ複合触媒、Ｎｉ触媒、Ｐｔ－Ｒｈ複合触媒の順に、改質反応に対する触媒能が高くなる。 The reforming catalyst has higher catalytic ability for the reforming reaction in the order of Ru catalyst, Ru—Pt composite catalyst, Ni catalyst, and Pt—Rh composite catalyst under the same use conditions.
　よって、本実施例では、Ｒｕ触媒＞Ｒｕ－Ｐｔ複合触媒＞Ｎｉ触媒＞Ｐｔ－Ｒｈ複合触媒という改質反応に対する触媒能の関係に基づいて、第１の改質触媒１の方が、第２の改質触媒２よりも改質反応に対する触媒能が高くなるよう、上記改質触媒を適宜選択する。但し、第１の改質触媒１として、Ｒｕ触媒を用い、第２の改質触媒２としてＰｔ－Ｒｈ複合触媒を用いる組み合わせは除くものとする。 Therefore, in the present embodiment, the first reforming catalyst 1 is the second reforming catalyst 1 based on the relation of the catalytic ability to the reforming reaction of Ru catalyst> Ru—Pt composite catalyst> Ni catalyst> Pt—Rh composite catalyst. The reforming catalyst is appropriately selected so that the catalytic ability for the reforming reaction is higher than that of the reforming catalyst 2. However, a combination using a Ru catalyst as the first reforming catalyst 1 and a Pt—Rh composite catalyst as the second reforming catalyst 2 is excluded.
　具体的には、第１の改質触媒１として、Ｒｕ触媒を用い、第２の改質触媒２として、Ｎｉ触媒を用いてもよい。また、第１の改質触媒１として、Ｒｕ触媒を用い、第２の改質触媒２として、Ｐｔ触媒を用いてもよい。また、第１の改質触媒１として、Ｒｕ－Ｐｔ複合触媒を用い、第２の改質触媒２として、Ｐｔ－Ｒｈ複合触媒を用いてもよい。 Specifically, a Ru catalyst may be used as the first reforming catalyst 1, and a Ni catalyst may be used as the second reforming catalyst 2. Further, a Ru catalyst may be used as the first reforming catalyst 1, and a Pt catalyst may be used as the second reforming catalyst 2. Further, a Ru—Pt composite catalyst may be used as the first reforming catalyst 1, and a Pt—Rh composite catalyst may be used as the second reforming catalyst 2.
　なお、上記の改質触媒の組合せは、例示であって、本例に限定されない。例えば、３種類以上の触媒金属を備える改質触媒を改質反応に対する触媒能の高い順に、改質器の上流側から順番に配設してもよい。
（実施の形態２）
　本実施の形態の燃料電池システムの運転方法は、実施の形態１および実施例１－７のいずれかの水素含有ガスの生成方法で生成された水素含有ガスを用いて燃料電池が発電するステップを備える。 The combination of the above reforming catalysts is an example, and is not limited to this example. For example, you may arrange | position the reforming catalyst provided with 3 or more types of catalyst metals in order from the upstream of a reformer in order with a high catalytic ability with respect to a reforming reaction.
(Embodiment 2)
The operation method of the fuel cell system according to the present embodiment includes a step in which the fuel cell generates power using the hydrogen-containing gas generated by the hydrogen-containing gas generation method according to any one of the first embodiment and Example 1-7. Prepare.
　実施の形態１および実施例１－７のいずれかの水素含有ガスの生成方法により、従来よりもアンモニアの生成を抑えて水素含有ガスを生成し得る。 By the method for producing a hydrogen-containing gas according to any one of Embodiment 1 and Examples 1-7, it is possible to produce a hydrogen-containing gas while suppressing the production of ammonia as compared with the conventional method.
　従って、従来例よりも燃料電池の性能低下を抑制し得る。 Therefore, the performance degradation of the fuel cell can be suppressed as compared with the conventional example.
　図３は、実施の形態２の燃料電池システムの運転方法に用いる燃料電池システムの概略構成の一例を示す図である。 FIG. 3 is a diagram showing an example of a schematic configuration of a fuel cell system used in the operation method of the fuel cell system of the second embodiment.
　図３に示す例では、燃料電池システム２００は、改質器１００と、燃料電池１０１とを備える。燃料電池１０１は、改質器１００より供給される水素含有ガスを用いて発電する燃料電池である。燃料電池１０１は、いずれの種類の燃料電池であってもよく、例えば、高分子電解質形燃料電池（ＰＥＦＣ）、固体酸化物形燃料電池またはりん酸形燃料電池等を用いることができる。 In the example shown in FIG. 3, the fuel cell system 200 includes a reformer 100 and a fuel cell 101. The fuel cell 101 is a fuel cell that generates power using the hydrogen-containing gas supplied from the reformer 100. The fuel cell 101 may be any type of fuel cell. For example, a polymer electrolyte fuel cell (PEFC), a solid oxide fuel cell, or a phosphoric acid fuel cell may be used.
　発電運転時において、燃料電池システム２００は、改質器１００から供給される水素含有ガスを用いて発電する。なお、燃料電池１０１の発電の動作は公知である。よって、詳細な説明は省略する。 During the power generation operation, the fuel cell system 200 generates power using the hydrogen-containing gas supplied from the reformer 100. The power generation operation of the fuel cell 101 is known. Therefore, detailed description is omitted.
　上記説明から、当業者にとっては、本発明の多くの改良や他の実施の形態が明らかである。従って、上記説明は、例示としてのみ解釈されるべきであり、本発明を実行する最良の態様を当業者に教示する目的で提供されたものである。本発明の精神を逸脱することなく、その構造及び／又は機能の詳細を実質的に変更できる。 From the above description, many modifications and other embodiments of the present invention are apparent to persons skilled in the art. Accordingly, the foregoing description should be construed as illustrative only and is provided for the purpose of teaching those skilled in the art the best mode of carrying out the invention. The details of the structure and / or function may be substantially changed without departing from the spirit of the invention.
　本発明の一態様は、従来よりもアンモニアの生成を抑えて水素含有ガスを生成し得る。 One embodiment of the present invention can generate a hydrogen-containing gas while suppressing the generation of ammonia as compared with the conventional one.
　１　第１の改質触媒
　２　第２の改質触媒
　１００　改質器
　１０１　燃料電池
　２００　燃料電池システム DESCRIPTION OF SYMBOLS 1 1st reforming catalyst 2 2nd reforming catalyst 100 Reformer 101 Fuel cell 200 Fuel cell system

Claims (11)

  1. 窒素分子及び窒素含有化合物の少なくともいずれか一方を含む原料を、第１の改質触媒を通過させるステップと、
    第１の改質触媒よりも下流に配設され、前記第１の改質触媒よりも改質反応に対する単位量当りの触媒能が低い第２の改質触媒を通過させるステップと、を備える水素含有ガスの生成方法。     Passing a raw material containing at least one of nitrogen molecules and a nitrogen-containing compound through a first reforming catalyst;
    Passing through a second reforming catalyst that is disposed downstream of the first reforming catalyst and has a lower catalytic ability per unit amount for the reforming reaction than the first reforming catalyst. Generation method of contained gas.
  2. 第１の改質触媒と第２の改質触媒とが、同一の触媒金属を備える請求項１に記載の水素含有ガスの生成方法。 The method for producing a hydrogen-containing gas according to claim 1, wherein the first reforming catalyst and the second reforming catalyst comprise the same catalyst metal.
  3. 第２の改質触媒の単位体積当たりの触媒金属の含有量が、第１の改質触媒のそれよりも少ない請求項２記載の水素含有ガスの生成方法。 The method for producing a hydrogen-containing gas according to claim 2, wherein the content of the catalyst metal per unit volume of the second reforming catalyst is less than that of the first reforming catalyst.
  4. 第２の改質触媒の比表面積は、第１の改質触媒のそれよりも小さい請求項２記載の水素含有ガスの生成方法。 The method for producing a hydrogen-containing gas according to claim 2, wherein the specific surface area of the second reforming catalyst is smaller than that of the first reforming catalyst.
  5. 　第２の改質触媒に含まれる触媒金属を担持する第２の担体は、第１の改質触媒に含まれる触媒金属を担持する第１の担体よりも改質反応に対する担体効果が低い、請求項１－４のいずれかに記載の水素含有ガスの生成方法。 The second carrier carrying the catalyst metal contained in the second reforming catalyst has a lower carrier effect on the reforming reaction than the first carrier carrying the catalyst metal contained in the first reforming catalyst. Item 5. The method for producing a hydrogen-containing gas according to any one of Items 1-4.
  6. 第１の改質触媒と第２の改質触媒とが、触媒金属としてＲｕを含有する触媒である請求項２－５のいずれかに記載の水素含有ガスの生成方法。 6. The method for producing a hydrogen-containing gas according to claim 2, wherein the first reforming catalyst and the second reforming catalyst are catalysts containing Ru as a catalyst metal.
  7. 第１の改質触媒と第２の改質触媒とが、触媒金属としてＮｉを含有する触媒である請求項２－５のいずれかに記載の水素含有ガスの生成方法。 6. The method for producing a hydrogen-containing gas according to claim 2, wherein the first reforming catalyst and the second reforming catalyst are catalysts containing Ni as a catalyst metal.
  8. 第１の改質触媒と第２の改質触媒とが分割されている請求項１－７のいずれかに記載の水素含有ガスの生成方法。 The method for producing a hydrogen-containing gas according to claim 1, wherein the first reforming catalyst and the second reforming catalyst are divided.
  9. 第２の改質触媒は、第１の改質触媒よりも触媒量が多い請求項１－７のいずれかに記載の水素含有ガスの生成方法。 The method for producing a hydrogen-containing gas according to any one of claims 1 to 7, wherein the second reforming catalyst has a larger catalyst amount than the first reforming catalyst.
  10. 　前記第２の改質触媒の温度は、前記第１の改質触媒の温度よりも高い、請求項１－９のいずれかに記載の水素含有ガスの生成方法。 The method for producing a hydrogen-containing gas according to any one of claims 1 to 9, wherein the temperature of the second reforming catalyst is higher than the temperature of the first reforming catalyst.
  11. 　請求項１－１０のいずれかに記載の水素含有ガスの生成方法で生成された水素含有ガスを用いて燃料電池が発電するステップを備える燃料電池システムの運転方法。 A method for operating a fuel cell system, comprising: a step of generating power by a fuel cell using the hydrogen-containing gas produced by the method for producing a hydrogen-containing gas according to any one of claims 1-10.
PCT/JP2012/005305 2011-09-22 2012-08-24 Process for generating hydrogen-containing gas and method for operating fuel cell system WO2013042314A1 (en)

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