WO2002059038A1 - Dispositif de purification d'hydrogene et systeme de generation de puissance a pile a combustible - Google Patents
Dispositif de purification d'hydrogene et systeme de generation de puissance a pile a combustible Download PDFInfo
- Publication number
- WO2002059038A1 WO2002059038A1 PCT/JP2002/000487 JP0200487W WO02059038A1 WO 2002059038 A1 WO2002059038 A1 WO 2002059038A1 JP 0200487 W JP0200487 W JP 0200487W WO 02059038 A1 WO02059038 A1 WO 02059038A1
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- Prior art keywords
- catalyst
- hydrogen
- oxide
- carbon monoxide
- reaction
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- C01B2203/16—Controlling the process
- C01B2203/1609—Shutting down the process
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/16—Controlling the process
- C01B2203/1614—Controlling the temperature
- C01B2203/1619—Measuring the temperature
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/16—Controlling the process
- C01B2203/1642—Controlling the product
- C01B2203/1647—Controlling the amount of the product
- C01B2203/1652—Measuring the amount of product
- C01B2203/1661—Measuring the amount of product the product being carbon monoxide
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/16—Controlling the process
- C01B2203/1642—Controlling the product
- C01B2203/1671—Controlling the composition of the product
- C01B2203/1676—Measuring the composition of the product
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- 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
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- 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
- Y02P20/10—Process efficiency
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- 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 hydrogen purifying apparatus for purifying a reformed gas containing hydrogen as a main component and containing carbon monoxide (hereinafter referred to as c ⁇ ) to provide high-purity hydrogen gas.
- the present invention also relates to a hydrogen supply device such as a polymer electrolyte fuel cell using hydrogen as a fuel. '' Background technology
- a fuel cell cogeneration system with high power generation efficiency and high overall efficiency has attracted attention as a distributed power generation device that effectively uses energy.
- One of the methods for generating hydrogen is a steam reforming method.
- a hydrogen source for fuel cells and other fuels raw materials such as natural gas, LPG, naphtha, gasoline, kerosene, and other hydrocarbons, alcohols such as methanol, and ethers are mixed with water to form a reforming catalyst.
- the reformed gas obtained by the steam reforming reaction in the section is used.
- the Pt catalyst used for the fuel cell electrode may be poisoned by CO contained in the reformed gas. When poisoning of the Pt catalyst occurs, hydrogen The reaction is hindered, and the power generation efficiency of the fuel cell is significantly reduced. Therefore, it is necessary to remove CO to 100 ppm or less, preferably 10 ppm or less, using a hydrogen purifier.
- CO-shifting catalysts have used copper-zinc based catalysts and copper-chromium-based catalysts that can be used at 150-300 ° C as low-temperature CO shifting catalysts.
- copper-zinc based catalysts and copper-chromium-based catalysts that can be used at 150-300 ° C as low-temperature CO shifting catalysts.
- iron-chromium catalysts that function at 300 ° C or higher are used.
- these CO shift catalysts can be used only as low-temperature CO shift catalysts or as a combination of high-temperature CO shift catalysts and low-temperature CO shift catalysts. Combination Had been used.
- the CO shift reaction is an equilibrium reaction that does not easily proceed in the direction of reducing the CO concentration in the high-temperature region.
- the CO concentration is reduced to 1% by volume. It was difficult to: As a result, the purification efficiency of the CO purification section connected later may be reduced.
- the conventional technology has a problem that, for example, it takes a long time to start up the hydrogen purifier and the handling is complicated, so that it cannot be sufficiently applied to an application that repeatedly starts and stops. .
- the present invention has been made in consideration of the above-described conventional problems, and has as its object to provide, for example, a hydrogen purification apparatus that can easily be heated at the time of starting and has high CO purification efficiency.
- the present invention provides a hydrogen purifying apparatus which takes into consideration the above-mentioned conventional problems, for example, facilitates heating at startup, prevents methanation, and increases the efficiency of the apparatus.
- the purpose is to:
- a first present invention is a hydrogen purifying apparatus comprising a carbon monoxide conversion catalyst for removing carbon monoxide from a reformed gas containing hydrogen, carbon monoxide, and steam,
- the carbon monoxide conversion catalyst includes a metal oxide containing at least one element selected from Fe, Cr, Ce, Mo, W, Re, and Cu; and Pt, Pd, Rh, and Ru.
- a hydrogen purification device containing at least one noble metal.
- the carbon monoxide conversion catalyst is (1) at least one selected from Fe, Cr, Ce, Mo, W, Re, and Cu.
- the hydrogen purification apparatus of the first aspect of the present invention which contains an element, a composite oxide in which other elements are composited, and (2) at least one noble metal of Pt, Pd, Rh, and Ru is there.
- the composite oxide is formed by complexing at least one of Mo, W, and Re with Zr, and Mo, W, and Re are A hydrogen purification apparatus according to a second aspect of the present invention, wherein the hydrogen purification apparatus contains a higher atomic percentage than the noble metal contained in the composite oxide.
- the composite oxide forms a solid solution. This is the third embodiment of the hydrogen purification apparatus of the present invention.
- the carbon monoxide conversion catalyst is selected from the group consisting of (1) Fe, Cr, Ce, Re, Mo, W, and Cu.
- the hydrogen purification apparatus according to the second invention wherein at least one of the elements and (2) at least one noble metal of Pt, Pd, Rh, and Ru are ion-exchanged or supported.
- the carbon monoxide conversion catalyst comprises: the metal oxide or the composite oxide; and at least one noble metal of Pt, Pd, Rh, and Ru. And a zeolite is further mixed in the hydrogen purification apparatus according to the second aspect of the present invention.
- the present invention seventh (corresponding to claim 7), the Zeorai metropolitan silica and alumina as a main component, the fifth or sixth invention of S i O2 / A 1 2 ⁇ 3 ratio is 4 or more It is a hydrogen purifier.
- the zeolite is a fifth, sixth or fifth type selected from a Y-type, an L-type, a mordenite-type, a ZSM-5-type and a beta-type structure.
- 7 is a hydrogen purification apparatus of the present invention No. 7.
- a ninth aspect of the present invention is that the composite oxide is composed of hydrogen and Fe of the second aspect of the present invention composed of Fe and Cr, 6 and 1, or Fe, Cr and Ni. It is a purification device.
- a tenth aspect of the present invention is the hydrogen purification apparatus according to the first aspect, wherein the metal oxide is iron oxide, and the particle size of the metal oxide is from 1011111 to 1 ⁇ . .
- the metal oxide is iron oxide
- the F e 2 ⁇ 3 and F e 3 ⁇ 4 of the first invention composed of at least one It is a hydrogen purifier.
- a twelfth aspect of the present invention (corresponding to claim 12) is that the iron oxide has magnetism A tenth or eleventh hydrogen purification apparatus according to the present invention.
- a thirteenth aspect of the present invention is a fuel cell power generation system using the carbon monoxide shift converter catalyst according to any one of the first to twelfth aspects of the present invention.
- FIG. 1 is a schematic longitudinal sectional view showing a configuration of a hydrogen generator including a hydrogen purifier according to Embodiments 1, 3, and 5 of the present invention.
- FIG. 2 is a schematic vertical sectional view showing a configuration of a hydrogen generator including a hydrogen purifier according to Embodiments 2 and 6 of the present invention.
- FIG. 3 is a schematic vertical sectional view showing a configuration of a hydrogen generator including a hydrogen purifier according to Embodiment 4 of the present invention.
- FIG. 4 is a schematic vertical sectional view showing a configuration of a hydrogen generator including a hydrogen purifier according to Embodiment 7 of the present invention.
- FIG. 5 is a schematic diagram showing a configuration of a fuel cell power generator incorporating the hydrogen purifier of the present invention.
- FIG. 1 is a schematic longitudinal sectional view showing the configuration of the hydrogen purifying apparatus according to the present embodiment.
- reference numeral 1 denotes a CO conversion catalyst (hereinafter, also simply referred to as a catalyst), which is installed inside the reaction chamber 2.
- Reference numeral 3 denotes a reformed gas inlet from which reformed gas is introduced. The reformed gas reacted in the CO conversion catalyst 1 is discharged from the reformed gas outlet 4.
- a diffusion plate 5 is provided upstream of the catalyst 1 so that the reformed gas flows uniformly. Further, in order to keep the reaction chamber 2 at a constant temperature, the outer periphery of a necessary portion was covered with a heat insulating material 6 made of ceramic wool.
- the catalyst body 1 was prepared by coating a cordierite honeycomb with a catalyst in which Pt was supported on a composite oxide of zirconium (hereinafter referred to as Zr) and molybdenum (hereinafter referred to as Mo '). Using.
- Fuels used to generate the reformed gas to be supplied to the hydrogen purifier include natural gas, methanol, gasoline, etc.
- the reforming method is also the steam reforming that adds water vapor, and the part that adds air. Although there is reforming, etc., here we describe the case where natural gas is reformed by steam reforming. You.
- composition of the reformed gas when natural gas is subjected to steam reforming varies slightly depending on the temperature of the reforming catalyst, but as an average value excluding steam, about 80% by volume of hydrogen, carbon dioxide, Each contains about 10% by volume of carbon monoxide.
- the natural gas reforming reaction is carried out at about 500 to 800 ° C, while the shift reaction in which CO and steam react is performed at about 150 to 350 ° C.
- the quality gas is supplied after cooling before the reformed gas inlet 3.
- the C 2 O concentration after passing through the C 0 conversion catalyst 1 is reduced to about 0.5% by volume, and is discharged from the reformed gas outlet 4.
- the CO conversion process is a temperature-dependent equilibrium reaction, and the lower the temperature, the lower the CO concentration.
- the reaction rate on the catalyst decreases. Therefore, there is a temperature at which the CO concentration reaches a minimum.
- Copper-based conversion catalysts such as copper-zinc catalysts and copper-chromium catalysts used as CO conversion catalysts in conventional hydrogen purifiers can perform CO conversion at low temperatures of 150 to 250 ° C. Depending on the conditions, the CO concentration can be reduced to several hundred to 1,000 ppm.
- the copper-based catalyst needs to be activated by flowing a reducing gas such as hydrogen or reformed gas at the start-up of the apparatus after the copper-based catalyst is charged into the reactor, and has a heat resistance of about 300 ° C. Low. Therefore, it is necessary to dilute the reducing gas with an inert gas or the like to supply it, or to gradually react it at a small flow rate so that the heat of reaction during activation does not exceed the heat resistance temperature, and it is necessary to take a long time for the reaction. You. Also, when starting up the equipment, it is necessary to heat it slowly and for a long time so that the temperature does not exceed the heat-resistant temperature due to overheating. There are many problems with applications that return.
- a reducing gas such as hydrogen or reformed gas
- the noble metal catalyst Pt is used for a part of the catalyst body 1 and has extremely high heat resistance as compared with the copper-based catalyst. Even when the temperature sometimes rises to about 500 ° C, there is no significant deterioration of the catalyst. In addition, there is no need to perform a long-time reduction treatment unlike the copper-based catalyst. Also, even if air is mixed in when the device is stopped, the catalyst deteriorates less than the copper catalyst.
- Precious metal catalysts containing Pt, Pd, Rh, Ru, and the like as active components have relatively low activity selectivity due to high activity. Therefore, depending on the conditions, the methane conversion reaction of CO or carbon dioxide may also proceed as a side reaction of the CO conversion reaction, and the consumption of hydrogen due to the progress of the methanation reaction may reduce the efficiency of the entire system Is concerned.
- the methanation reaction becomes more remarkable as the temperature becomes higher.
- the methane generation rate differs depending on the type of the noble metal. This is because the CO adsorption mechanism differs depending on the type of noble metal.Pd, Rh and Ru, which have a CO adsorption mechanism that facilitates the methanation reaction, generate methane at a relatively low temperature and cause the CO shift reaction.
- the temperature range in which the process can be performed is narrowed.
- the Pt catalyst used in the present embodiment hardly causes a methanation reaction and can perform a CO shift reaction in a wide temperature range. Therefore, a large amount of hydrogen is not consumed due to the progress of the methanation reaction, and the hydrogen purifier of the present embodiment can operate efficiently.
- the activity of the Pt catalyst for the CO conversion reaction is improved, and the methanation reaction can be suppressed. This is due to the effect of changing the oxidation state of the Pt catalyst to a state in which the shift reaction proceeds easily.
- the amount of Mo added is preferably equal to or more than the amount of Pt supported. Although the catalytic activity improves as the amount of Pt supported increases, the effect of merely increasing the amount of Pt cannot be obtained unless Mo is present in the same amount or more with respect to Pt.
- molybdenum oxide has a lower heat resistance than a carrier such as zirconia, and when used at a temperature exceeding 600 ° C, the specific surface area may decrease and catalytic activity may decrease. There is. Also, since it is slightly water-soluble, it also reduces the possibility of Mo escaping over long periods of use.
- the catalyst carrier for example, a composite oxide in which Mo is combined with Zr is used as the catalyst carrier, so that the stability of the catalyst carrier is improved and the activity of the catalyst is hardly reduced.
- the ratio of Mo and Zr the lower the Mo (that is, the higher the Zr), the higher the heat resistance and the more stable.
- the content of Mo is preferably at least 1 atomic%.
- the Mo content is higher than 90 atomic%, almost the same performance as that of molybdenum oxide can be obtained.
- the carrier is composed of a composite oxide in which at least one of Mo, W, and Re and Zr are composited, and oxygen in the composite oxide is excluded.
- the same effect as described above can be obtained even when the composition ratio of the elements is 1 to 90 atomic percent with respect to the entire composite oxide.
- the method of compounding Zr with Mo is not particularly limited, and examples thereof include a coprecipitation method, a sol-gel method, and an alkoxide method.
- the zirconia may be impregnated with a Mo salt solution.
- the BET specific surface area is a specific surface area determined by a known measurement method in which nitrogen is adsorbed on a powder.
- the upper limit of the BET specific surface area is not particularly limited, and a high activity can be obtained similarly even when the surface area is 100 to 200 square meters per lg. The effect of increasing the surface area is reduced. If the BET specific surface area of the metal oxide / composite metal oxide is less than 10 square meters per 1 g, Pt is not sufficiently adsorbed and the dispersion of Pt is reduced. No catalytic activity is obtained. If the amount of Pt supported is reduced in order to reduce the particle size of Pt, the number of active sites decreases, and sufficient activity cannot be obtained.
- a composite oxide in which Mo is compounded with respect to Zr is used.
- Mo tungsten (W) or rhenium (R e) may be compounded. Similar effects can be obtained. Since these elements have chemical properties similar to Mo, the effect of addition is the same as Mo. The same effect can be obtained by using these additional elements in combination.
- the shape of the catalyst body is cordierite honeycomb, but the same performance can be obtained even if the shape of the carrier is pelletized and impregnated with a Pt salt to produce a CO conversion catalyst body. Is obtained. (Embodiment 2)
- the catalyst body is divided into two stages and a cooling unit is provided in the middle of the catalyst body, and most of the operation and effect are similar to those of the first embodiment. Therefore, the present embodiment will be described focusing on the different points.
- FIG. 2 is a schematic vertical sectional view showing the configuration of the hydrogen purifier according to the present embodiment.
- the catalyst body is divided into the first catalyst body 11 and the second catalyst body 13, a cooling section is provided in the middle, and the reformed gas is cooled by the cooling fan 19, thereby reducing the CO concentration with a small amount of catalyst can do. Since the CO conversion reaction is an exothermic reaction, the heat of reaction generated in the upstream part of the catalyst is transferred to the downstream part by the reformed gas. For this reason, the temperature of the catalyst body is likely to be higher in the downstream portion, and even if the C0 concentration is sufficiently reduced in the upstream portion, the C0 concentration increases due to the reversion reaction in the high-temperature downstream portion.
- the reverse reaction can be suppressed by lowering the temperature of the second catalyst body 13 on the downstream side than that of the first catalyst body 11.
- a two-stage configuration is used.
- the number of stages there is no particular limitation on the number of stages, and high characteristics can be obtained as long as the catalyst bodies in each stage can be controlled to optimal temperatures.
- the carbon monoxide shift catalyst is divided into a plurality of stages, and each of the split carbon monoxide shift catalysts is disposed upstream of the reformed gas path.
- a cooling unit for cooling at least one of the reformed gas between the carbon monoxide shift catalysts, and a radiator for releasing the heat of the reformed gas may be provided, and even with such a configuration, the same effect as described above can be obtained.
- cooling fan was used as the cooling means, cooling with water may be used.
- examples 1 and 2 will be described below as examples corresponding to the first embodiment.
- a reformed gas containing 8% by volume of carbon monoxide, 8% by volume of carbon dioxide, 20% by volume of water vapor, and the balance of hydrogen was introduced at a flow rate of 10 liters per minute.
- the composition of the gas discharged from the reformed gas outlet 4 was measured by gas chromatography.
- a conventional copper-zinc catalyst was used as the catalyst body 1 in place of the above-mentioned composite oxide supporting Pt, and the reaction chamber 2 shown in FIG. It was installed in.
- a reformed gas containing 8% by volume of carbon monoxide, 8% by volume of carbon dioxide, 20% by volume of steam, and the balance of hydrogen was introduced at a flow rate of 10 liters per minute.
- the composition of the gas discharged from the reformed gas outlet 4 was measured by gas chromatography, and the lowest value of the CO concentration was 0.08% by volume. Met.
- the operation of restarting after restarting the device was repeated 10 times, and the change in the activity of the catalyst was confirmed by measuring the CO concentration.
- the lowest value of the CO concentration was 4% by volume.
- the CO concentration after starting and stopping 10 times is significantly higher than that in the case of using the catalyst in the aforementioned example. Therefore, as described above, it has been confirmed that the hydrogen purifier of the present invention is not easily affected by oxygen contamination and the like and is stably operated for a long period of time even when the operation is repeatedly started and stopped. .
- the present invention provides, for example, a reformed gas supply unit for supplying a reformed gas containing at least hydrogen gas, carbon monoxide, and steam;
- a hydrogen purifier comprising a reaction chamber provided with a carbon monoxide shift catalyst located downstream, wherein the carbon monoxide shift catalyst is at least Mo or W or R with respect to Zr, for example. Let e be at least Pt supported on the composite oxide.
- the composition ratio in the composite oxide is preferably such that Mo is 1 to 90 atomic% and the remaining force is r.
- Pt is supported on the composite oxide of the present invention.
- the present invention is not limited to this.
- Pt, Pd, Rh, Ru At least one of them.
- a noble metal catalyst containing Pd, Rh, Ru, or the like as an active component may cause the methanation reaction to proceed as described above. Therefore, it is most preferable to use Pt. Therefore, even when Pd, Rh, Ru or the like is used, at least Pt is supported on the composite oxide, and it is desirable that these are added mainly with Pt.
- the hydrogen purification apparatus of the present invention has improved durability of the CO conversion catalyst, and can operate stably even when the apparatus is repeatedly started and stopped.
- reference numeral 1 denotes a CO conversion catalyst (hereinafter, also simply referred to as a catalyst), which is installed inside the reaction chamber 2.
- Reference numeral 3 denotes a reformed gas inlet, through which reformed gas is introduced. The reformed gas reacted by the catalyst 1 is discharged from the reformed gas outlet 4.
- a diffusion plate 5 is provided upstream of the catalyst 1 so that the reformed gas flows uniformly. Further, in order to keep the reactor at a constant temperature, necessary portions are covered with a heat insulating material 6 made of ceramic wool.
- the catalyst body 1 S i 0 2 / A l 2 ⁇ 3 two 5 (silica one alumina ratio faujasite site type 4 or more of) Y-type zeolites (molar ratio) in the C e It was prepared by coating a cordierite honeycomb with one carrying Pt.
- Fuels used to generate the reformed gas to be supplied to the hydrogen purifier include natural gas, methanol, gasoline, etc.
- the reforming methods are steam reforming with steam and partial reforming with air. This section describes the case where natural gas is reformed by steam reforming.
- the composition of the reformed gas when natural gas is subjected to steam reforming varies slightly depending on the temperature of the reforming catalyst, but as an average value excluding steam, about 80% by volume of hydrogen, carbon dioxide, Each contains about 10% by volume of carbon monoxide.
- the reforming reaction of natural gas is performed at about 500 to 800 ° C, while the conversion reaction of CO and water vapor is performed at about 150 to 350 ° C.
- the quality gas is supplied after cooling before the reformed gas inlet 3.
- the CO concentration after passing through the contact medium 1 is reduced to about 1% by volume, and the reformed gas outlet 4 Is more exhausted.
- the CO conversion process is a temperature-dependent equilibrium reaction, and the lower the temperature, the lower the CO concentration.
- the reaction rate on the catalyst decreases. Therefore, there is a temperature at which the CO concentration reaches a minimum.
- Copper-based conversion catalysts such as copper-zinc catalyst and copper-chromium catalyst used as CO conversion catalysts in conventional hydrogen purifiers can perform CO conversion at a low temperature of 150 to 250 ° C. Depending on the conditions, the CO concentration can be reduced to several hundred to 1,000 ppm.
- the copper-based catalyst needs to be activated by flowing a reducing gas such as hydrogen / reforming gas after being charged into the reactor, and has a low heat resistance of about 300 ° C. Therefore, it is necessary to dilute the reducing gas with an inert gas or the like or to supply it with a small amount of gas so that the reaction heat at the time of activation does not exceed the heat resistant temperature. Cost. Also, when starting up the equipment, it is necessary to heat it slowly and for a long time so that the temperature does not exceed the heat-resistant temperature due to overheating. Many.
- a reducing gas such as hydrogen / reforming gas
- the catalyst body 1 a catalyst body containing a noble metal as an active component is used as the catalyst body 1, and the catalyst is greatly deteriorated even when the apparatus is started up to about 500 ° C. There is nothing.
- the heat resistance of the catalyst body 1 is high, it is not necessary to perform the reduction treatment for a long time in order to suppress heat generation due to the heat of the reduction reaction as in the case of the copper-based catalyst. Also, even if air is mixed in when the device is stopped, the catalyst deteriorates less than the copper catalyst.
- the active ingredient is supported in a highly dispersed manner, and the interaction between the carrier zeolite and the noble metal is achieved. Is large, so that deterioration is also suppressed.
- Zeolite is generally composed mainly of silica and alumina.
- Precious metal catalysts containing Pt ', Pd, Rh, Ru, and the like as active components have high activity and relatively low reaction selectivity. Therefore, depending on the conditions, the methane conversion reaction of CO or carbon dioxide may also proceed as a side reaction of the CO conversion reaction, and the consumption of hydrogen due to the progress of the methanation reaction may reduce the efficiency of the entire system Is concerned.
- the methanation reaction becomes more pronounced as the temperature increases, but the methane production rate differs depending on the type of noble metal. This is because the mechanism of CO adsorption differs depending on the type of precious metal.Pd, which has a mechanism for adsorbing CO, which promotes the methanation reaction, emits methane even at relatively low temperatures. As a result, the temperature range in which the CO shift reaction can be performed is narrowed.
- the Pt catalyst used in the present embodiment hardly causes a methanation reaction and can perform a CO shift reaction in a wide temperature range. Therefore, a large amount of hydrogen is not consumed by the progress of the methanation reaction, and the hydrogen purifying apparatus of the present embodiment is not consumed. The device can operate efficiently.
- the amount of the noble metal to be supported may be any amount as long as the noble metal has a high degree of dispersion and can exhibit the required activity. As the noble metal content increases, the noble metal particles become larger and the amount of noble metal that does not contribute to the reaction increases. Conversely, if the noble metal content is low, sufficient activity cannot be obtained. For this reason, it is preferably between 0.1% by weight and 5% by weight with respect to the catalyst carrier, like a normal noble metal catalyst for combustion and exhaust gas purification.
- Ce has the effect of suppressing the methanation reaction on the noble metal catalyst.
- alumina, silica, titanium oxide or the like is used as a catalyst carrier for the noble metal catalyst.
- the methanation reaction easily proceeds in a temperature range of 300 ° C or higher.
- methanation reaction hardly proceeds even at a high temperature of about 450 ° C. Similar effects can be obtained by adding a transition metal selected from Cu, Fe, Cr, Re, Mo, and W in addition to Ce.
- the added amount of Cu, Fe, Cr, Ce, Re, Mo, and W is preferably an amount capable of being efficiently supported in the pores of zeolite, and 0.5 to 10% by weight is most effective. is there.
- zeolite having a Y-type structure was used.
- the structure is not particularly limited as long as the zeolite has sufficiently large pores for a reaction gas (CO and water molecules).
- a reaction gas CO and water molecules.
- Mordenite, ZSM-5, and beta structures These have pores of 0.5 to 1 nm, and active sites in the pores can function effectively, so that high activity can be obtained.
- the shape of the catalyst body is a cordierite honeycomb coated with a catalyst, but the zeolite shape is a pellet shape, and the catalyst is impregnated with a noble metal salt or the like, and the CO conversion catalyst body is formed. Even if it is produced, a CO shift catalyst having the same performance can be obtained.
- zeolite supports Ce and Pt, but the same effect can be obtained by mixing zeolite with a noble metal supported on a metal oxide such as cerium oxide.
- Embodiment 4 is similar to Embodiment 3 except that an air supply unit 25 (or an oxidizing gas supply unit) is provided upstream of the catalyst body 21 as shown in FIG.
- FIG. 3 is a schematic sectional view showing the configuration of the hydrogen purifier according to the present embodiment.
- reference numeral 21 denotes a CO conversion catalyst (hereinafter, also simply referred to as a catalyst), which is installed inside the reaction chamber 22.
- 23 is a reformed gas inlet from which reformed gas is introduced. The reformed gas reacted by the catalyst 21 is discharged from the reformed gas outlet 24.
- a diffusion plate 26 is provided upstream of the catalyst body 21 so that the reformed gas flows uniformly. Further, in order to keep the reactor at a constant temperature, the outer periphery is covered with a heat insulating material 27 made of ceramic wool.
- the catalyst 21 By supplying air from the air supply unit 25, hydrogen or carbon monoxide in the reformed gas is oxidized by the catalyst 21. Normally, when starting Water condenses on the catalyst until the temperature of 21 rises sufficiently, and the oxidation reaction does not proceed sufficiently. For this reason, it does not generate heat even when air is added, so it takes time to start up.
- the catalyst 21 contains hydrophobic zeolite, and the oxidation reaction occurs on the catalyst 21 even under the condition where a large amount of water vapor is contained, such as when the apparatus is started. Progresses, and the temperature of the catalyst body 21 rises quickly.
- the amount of air to be added varies depending on the device configuration and the like, and is not particularly limited. However, it is necessary to select an air amount at which the temperature of the catalyst rapidly rises and the temperature of the catalyst body does not excessively rise.
- the supplied air oxidizes Cu and generates heat at a temperature lower than the temperature at which the oxidation reaction of the catalyst starts, so that heat is generated.
- the temperature of the catalyst body 21 rises faster.
- silica one alumina ratio S i O 2 / A 1 2 ⁇ 3 5 Y-type zeolite preparative (referred to as Y in the table), C u, F e, C r, 1% by weight of Ce, Re, Mo, and W were supported, and 1% by weight of a noble metal (noble metal species is described in the table).
- silica one alumina ratio S i O 2 / A 1 2 ⁇ 3 5 in L-type, Morudenai preparative, ZSM 5 type, the beta zeolite preparative (in the table, respectively L, M, and ZSM 5,] 3 1) by weight, and 1% by weight of Pt. These were coated on a cordierite honeycomb and placed in the reaction chamber 2 shown in FIG.
- ⁇ -type zeolite can be obtained by using L-type, mordenite-type, ZSM5-type, and] 3-type zeolites.
- an air supply unit 14 is provided upstream of the catalyst body 21 and the air is supplied at a flow rate of 0.2 liter per minute while starting up in the same manner as in the fifth embodiment. The time was measured. Table 5 summarizes these results.
- Comparative Examples 2 to 4 are shown below as Comparative Examples corresponding to Examples: to 7.
- an oxide having the composition shown in Table 7 or a noble metal supported on 1% by weight of alumina, and 42 to 47 as the catalyst body 1 were used.
- an air supply unit 25 was provided upstream of the catalyst body 21 as shown in FIG. 3 and started in the same manner as in Comparative Example 3 while supplying air at a flow rate of 0.2 liter per minute. When the time was measured, it was 40 minutes.
- the complex oxide of iron and chromium that does not contain noble metals cannot reduce CO enough, and the copper-zinc catalyst has a high initial activity, but its activity decreases significantly after repeated start-stop.
- the activity is not reduced, but the methane concentration at 400 ° C. is high.
- the startup time was also shortened by using Zeolite.
- the hydrogen purification apparatus of the present invention has improved durability of the CO conversion catalyst, and operates stably even when the apparatus is repeatedly started and stopped. Startup time can also be reduced (Embodiment 5)
- reference numeral 1 denotes a CO conversion catalyst (hereinafter, also simply referred to as a catalyst). ), which is installed inside the reaction chamber 2.
- Reference numeral 3 denotes a reformed gas inlet from which reformed gas is introduced. The reformed gas reacted by the CO shift catalyst 1 is discharged from the reformed gas outlet 4.
- a diffusion plate 5 is provided upstream of the catalyst 1 so that the reformed gas flows uniformly. Further, in order to keep the reactor at a constant temperature, necessary portions are covered with a heat insulating material 6 made of ceramic wool.
- Fuels used to generate the reformed gas to be supplied to the hydrogen purifier include natural gas, methanol, gasoline, etc.
- the reforming method is also the steam reforming that adds water vapor, and the part that adds air. There is reforming, etc., but here, the case where natural gas is reformed by steam reforming will be described.
- composition of the reformed gas when natural gas is subjected to steam reforming varies slightly depending on the temperature of the reforming catalyst, but as an average value excluding steam, about 80% by volume of hydrogen, carbon dioxide, Each contains about 10% by volume of carbon monoxide.
- the natural gas reforming reaction is carried out at about 500 to 800 ° C, while the shift reaction in which CO and steam react is performed at about 150 to 350 ° C.
- the quality gas is supplied after cooling before the reformed gas inlet 3. After passing through the CO conversion catalyst 1, the CO concentration is reduced to about 1% by volume and discharged from the reforming gas outlet 4.
- CO shift reaction is an equilibrium reaction depending on temperature, The more the CO concentration can be reduced. On the other hand, at low temperatures, the reaction rate on the catalyst decreases. Therefore, there are temperatures where the CO concentration has a minimum.
- Copper-based conversion catalysts such as copper-zinc catalyst and copper-chromium catalyst used as co-transformation catalysts in conventional hydrogen purifiers can perform CO-transformation at low temperatures of 150 to 250 ° C. Depending on the conditions, the CO concentration can be reduced to several hundred to 1,000 ppm.
- copper-based catalysts need to be activated by flowing a reducing gas such as hydrogen / reformed gas after filling in a reactor, and have a heat resistance of 3%.
- a reducing gas such as hydrogen / reformed gas
- Cost when starting up the equipment, it is necessary to heat it slowly and for a long time so that the temperature does not exceed the heat resistance temperature due to overheating. Many.
- the catalyst body 1 uses Pt supported on a composite oxide of Fe and Cr having high heat resistance. Even at temperatures as high as ° C, the catalyst does not deteriorate significantly. Further, since the heat resistance of the catalyst body 1 is high, it is not necessary to perform the reduction treatment over a long period of time in order to suppress heat generation due to the heat of the reduction reaction, unlike a copper-based catalyst. Also, even if air is mixed in when the device is stopped, the catalyst deteriorates less than the copper catalyst.
- Oxides of Fe and Cr each show activity in the metamorphic reaction even when they are used alone.However, since the reaction rate is low, the reaction rate increases. It must be used at low space velocities (SV) with a catalyst. When used at high temperatures, the equilibrium concentration of CO is high and the CO is sufficiently low. It cannot be reduced. Also, if a large amount of catalyst is used, it becomes difficult to reduce the size of the apparatus. When Fe and Cr are combined, the heat resistance is improved and the oxidation-reduction of the oxide accompanying the reaction proceeds smoothly, so that the reaction speed is improved and the activity is increased even in a temperature range of about 350 ° C. As shown, the limit is to reduce CO to about 2% by volume, which is not sufficient.
- Precious metal catalysts containing Pt, Pd, Rh, Ru, and the like as active components have relatively low activity selectivity due to high activity. Therefore, depending on the conditions, the methane conversion reaction of CO or carbon dioxide may also proceed as a side reaction of the CO conversion reaction, and the consumption of hydrogen due to the progress of the methanation reaction may reduce the efficiency of the entire system Is concerned.
- the methanation reaction becomes more pronounced at higher temperatures, but the meta-generation rate varies depending on the type of noble metal. This is because the CO adsorption mechanism differs depending on the type of noble metal.Pd, Rh, and Ru, which have a CO adsorption mechanism that facilitates the methanation reaction, generate methane even at relatively low temperatures and produce CO
- the temperature range in which the reaction can be performed becomes narrow.
- the Pt catalyst used in the present embodiment hardly causes a methanation reaction and can perform a CO shift reaction in a wide temperature range. Therefore, a large amount of hydrogen is not consumed by the progress of the methanation reaction, and the hydrogen purifying apparatus of the present embodiment can operate efficiently.
- noble metal catalysts include alumina, silica, titanium oxide, etc.
- the methanation reaction easily proceeds in a temperature range of 300 ° C or more.
- an oxide of Fe or Cr is used as a catalyst carrier, the methanation reaction hardly proceeds even at a high temperature of about 450 ° C.
- a composite oxide obtained by compounding (: 1: 1) into 6 is used as the catalyst carrier, so that the stability of the catalyst carrier is improved and the activity of the catalyst is hardly reduced.
- the activity increases as the amount of Cr decreases (that is, the amount of Fe increases), but the heat resistance decreases as the Cr content decreases. Therefore, the content of Cr is preferably at least 1 atomic% with respect to Fe. However, when the Cr content is higher than 50 atomic%, almost the same performance as that of chromium oxide can be obtained. That is, in the hydrogen purifying apparatus, when the composition ratio of elements excluding oxygen in the oxide is 1 to 50 atomic percent of Cr with respect to Fe, the same effect as described above can be obtained.
- the method of complexing Cr with Fe is not particularly limited, and examples thereof include a coprecipitation method, a sol-gel method, and an alkoxide method.
- the iron oxide may be impregnated with a solution of a Cr salt.
- a composite oxide in which Cr is compounded with Fe is used.
- a catalyst carrier having a high specific surface area such as alumina, silica alumina, or zirconia is used. The same effect can be obtained by using a composite of Cr.
- the catalyst body was formed by coating the catalyst on a cordierite honeycomb, but the carrier was formed into a pellet shape and impregnated with a Pt salt to prepare a CO conversion catalyst body.
- a CO shift catalyst having the same performance can be obtained.
- the amount of noble metal supported is such that noble metal has a high degree of dispersion and Any amount can be used as long as the activity can be exhibited.
- the noble metal content increases, the noble metal particles become larger and the amount of noble metal that does not contribute to the reaction increases. Conversely, if the noble metal content is low, sufficient activity cannot be obtained. For this reason, it is preferably between 0.1% by weight and 10% by weight with respect to the catalyst carrier, like a normal noble metal catalyst for combustion and exhaust gas purification.
- the catalyst body is divided into two stages, and a cooling unit is provided in the middle of the catalyst body.
- a cooling unit is provided in the middle of the catalyst body.
- FIG. 2 is a schematic vertical sectional view showing the configuration of the hydrogen purifier according to the present embodiment.
- the CO concentration can be reduced with a small amount of catalyst.
- the cooling unit in the example of Fig. 2, a plurality of pipes through which air passes are provided.
- a heat recovery unit may be provided instead of the cooling unit.
- the co-transformation reaction is an exothermic reaction
- the heat of reaction generated in the upstream part of the catalyst is transferred to the downstream part by the reformed gas.
- the temperature of the catalyst body is likely to be higher in the downstream portion, and even if the C0 concentration is sufficiently reduced in the upstream portion, the C0 concentration increases due to the reversion reaction in the high-temperature downstream portion. Therefore, the reverse reaction can be suppressed by lowering the temperature of the second catalyst body 13 on the downstream side than that of the first catalyst body 11.
- the reaction chamber is divided into the first reaction chamber 12 and the second reaction chamber 14, but the temperature of the reformed gas is located at an intermediate position between the first catalyst body 11 and the second catalyst body 13. It is not necessary to divide the reaction chamber if a means such as a radiation fin is provided as a means for reducing the temperature.
- the same type of catalyst is used for the first catalyst 11 and the second catalyst 13, but a second catalyst which is active at a lower temperature than the first catalyst is used.
- the second catalyst 13 may be any catalyst as long as it has a higher activity at low temperatures for the metamorphic reaction than the first catalyst.
- examples include a composite oxide of Zr and Ce supporting Pt.
- a copper zinc catalyst is preferred.
- the hydrogen purifier is a hydrogen purifier including a carbon monoxide shift catalyst for removing carbon monoxide from a reformed gas containing hydrogen, carbon monoxide, and steam, wherein the carbon monoxide shift catalyst is It is composed of a plurality of stages, at least one of which has an oxide containing at least one element of Fe and Cr and at least one of Pt, Pd, Rh and Ru A first catalyst body containing a noble metal is installed, and at least one lower stage of the first catalyst body is provided with a second catalyst body that is active at a lower temperature than the first catalyst body. In that case, the same effect can be obtained.
- the second catalyst body 13 may be one in which Pt is supported on an oxide containing at least one element of Zr, Ce, and A1, and in that case, the above-described second catalyst body 13 may also be used. The same effect can be obtained.
- the second catalyst body may contain at least Cu and Zn, and in such a case, the same effect as above can be obtained.
- Example 8 1% by weight of a noble metal (noble metal species is described in the table) was supported on metal oxides or composite oxides 1 to 10 having compositions shown in Table 8. This was coated on a Koji Elite honeycomb and placed in the reaction chamber 2 shown in FIG.
- a reformed gas containing 8% by volume of carbon monoxide, 8% by volume of carbon dioxide, 20% by volume of water vapor, and the balance of hydrogen was introduced at a flow rate of 10 liters per minute.
- the composition of the gas discharged from the reformed gas outlet 4 was measured by gas chromatography.
- a reformed gas consisting of 8% by volume of carbon monoxide, 8% by volume of carbon dioxide, 20% by volume of steam, and the balance of hydrogen was introduced at a flow rate of 10 liters per minute.
- the methane concentration in the gas after the reaction at the lowest value of the CO concentration and the temperature of the first catalyst 11 at 400 ° C. was 0.30% by volume and 0.005% by volume, respectively.
- an operation to re-Pi repeatedly started 1 0 times, by measuring the CO concentration O to confirm the activity variation of the catalyst rollers, 0. 3 0 volume 0 /. Met.
- Comparative Example 6 is described below as a comparative example corresponding to Examples 8 and 9. (Comparative Example 5)
- an oxide having a composition shown in Table 9 or a noble metal supported on 1% by weight of alumina, and 11 to 19 were used as the catalyst 1, As in Example 8, it was set in the reaction chamber 2 shown in FIG.
- a reformed gas containing 8% by volume of carbon monoxide, 8% by volume of carbon dioxide, 20% by volume of water vapor, and the balance of hydrogen was introduced at a flow rate of 10 liters per minute.
- the composition of the gas discharged from the reformed gas outlet 4 was measured by gas chromatography. Measure the minimum value of the CO concentration when the temperature is changed, the methane concentration in the gas after the reaction at a catalyst temperature of 400 ° C, and stop and restart the device 10 times. Then, the minimum value of the CO concentration was measured to confirm the change in the activity of the catalyst. Table 9 summarizes these results. .
- the hydrogen purification apparatus of the present invention has improved durability of the CO conversion catalyst, and can operate stably even when the apparatus is repeatedly started and stopped.
- FIG. 4 is a configuration diagram of a hydrogen purifying apparatus according to Embodiment 7 of the present invention.
- a reforming section 31, a reforming catalyst 32 contained in the reforming section 31, and a reforming catalyst 3 are shown.
- a hydrogen gas supply unit is provided by a raw material supply unit 3 that supplies raw materials to 2, a water supply unit 3 that supplies water to the reforming catalyst 32, and a reforming heating unit 35 that heats the reforming catalyst 32.
- Reference numeral 36 denotes a shift section to which the gas from the reforming section 31 is supplied, in which a shift catalyst body 37 is stored.
- the hydrogen gas whose carbon monoxide has been reduced in the shift unit 36 becomes hydrogen gas whose carbon monoxide concentration has been reduced to 100 ppm or less through the purification unit 38 in order to further reduce the carbon monoxide. .
- the supplied methane amount was set to 35 OLZ hours, and the heating amount was controlled by the reforming heating section 35 so that the temperature of the reforming catalyst 32 became about 700 ° C, and the water vapor reforming was performed.
- the reaction was allowed to proceed.
- the hydrogen gas after the reaction in the reforming section 31 was supplied to the shift section 36.
- a shift reaction occurs between the carbon monoxide in the hydrogen gas and water vapor on the shift catalyst 37.
- the invention described in the present embodiment is characterized in that a catalyst prepared by supporting Pt on an oxide of iron (hereinafter, referred to as Fe) is used as the conversion catalyst 37.
- the modified catalyst body 37 is formed by coating the present catalyst on cordierite honeycomb.
- Fe oxide as a carrier can suppress the formation of methanation and reduce carbon monoxide.
- the reason for this is that Fe has the effect of attracting the electrons of Pt, which makes the adsorption of Pt and carbon monoxide in the shift reaction process weaker than that of the catalysts used conventionally. . Therefore, carbon monoxide adsorbed on Pt reacts with water, and the carbon dioxide generated is easily desorbed. The adsorption of element does not become rate-limiting. As a result, methane production can be suppressed.
- Fe oxides are composed of Fe 2 ⁇ 3 or Z and Fe 3 ⁇ 4 , so that the shift reaction proceeds preferentially, and methane as a by-product of the reaction between carbon monoxide and hydrogen. Generation can be suppressed.
- the F e oxide is present in the form of F e 2 ⁇ 3, itself is reduced with carbon monoxide F e 3 0 4 and. Becomes a two Produces carbon oxide.
- F e 3 0 4 is oxidized by steam itself F e 2 ⁇ 3 next, to produce hydrogen.
- F e oxide is present in F e 2 0 3 or Z and F e 3 Rei_4 by F e oxide itself repeatedly redox cycle, priority shift reaction of carbon monoxide and hydrogen Can be progressed. As a result, methane production can be suppressed.
- the Fe oxide as a composite oxide of Cr or Z and Ni, it is possible to make the shift conversion catalyst excellent in durability.
- Fe oxides are subject to thermal degradation when exposed to high temperatures, resulting in reduced catalytic activity.
- Cr or Ni has the effect of suppressing thermal degradation of Fe at high temperatures, the catalyst activity can be maintained even after exposure to high temperatures.
- the presence of Cr and / or Ni oxide at the grain boundaries of the Fe oxide prevents thermal condensation of the Fe oxide particles, resulting in a metamorphosis compared to the Fe oxide alone. Thermal degradation of the medium can be suppressed.
- Fe oxide and Cr and / or Ni oxide form a solid solution to form a composite oxide, the movement, condensation, and growth of particles are reduced, and the thermal degradation of the metamorphic catalyst is further increased. Has the effect of suppressing
- the particle size of the Fe oxide also affects the reactivity. Since the particle size of Pt in the present catalyst is about 1 nm to 10 nm, the carrier for supporting Pt preferably has a particle size of Pt or more. On the other hand, if the particle size is smaller than 10 nm, it tends to agglomerate at a high temperature, which causes thermal degradation of the shift catalyst. Also, if the particle size of the Fe oxide is larger than 1 ⁇ m, the surface area is reduced, and the interaction force between the Fe oxide and Pt is reduced. In order for the reaction to proceed effectively, it is desirable to use a particle size smaller than ⁇ . In this embodiment, the Fe oxide having a particle diameter of 30 nm was used.
- the conversion catalyst 37 is also high when zeolite is used as a catalyst carrier and Fe is ion-exchanged and supported by Pt by impregnation. Catalyst activity is obtained.
- zeolite Since zeolite has a large surface area, the catalytic reaction area increases, and the catalytic activity improves.
- the ion exchange method as a loading method only replaces the acid sites in the zeolite, Fe can be loaded in a highly dispersed manner, leading to an improvement in catalytic activity.
- F e carried by replacing the acid sites in zeolite is an acidic substance having an acid site, and is easy to attract electrons of other materials. Therefore, since electrons of Pt carried later are attracted to F e, in the process of the shift reaction, the adsorbing power of carbon monoxide adsorbed on Pt with carbon atoms is weakened. As a result, as in the case where Pt is supported on the Fe oxide, the methanation reaction is suppressed and the shift reaction is allowed to proceed selectively, so that carbon monoxide can be effectively reduced.
- the same effect can be obtained by using oxides of A1, Si, Ce, Zr, and Ti instead of zeolite. These oxides can also easily increase the surface area and can be used as a carrier that easily supports Fe and Pt, so that the same effect can be obtained.
- a hydrogen purifying apparatus comprising: a gas supply unit that supplies a hydrogen gas containing at least water vapor and carbon monoxide; and a shift unit that has a shift catalyst that shifts carbon monoxide and steam in the hydrogen gas.
- the above-mentioned metamorphic catalyst body uses an oxide containing at least one element of A1, Si, Ce, Zr, and Ti as a catalyst carrier, and at least one of Cu, Zn, and Fe.
- a transition metal and at least one noble metal of Pt, Pd, Rh, and Ru may be supported.
- the catalyst carrier may be zeolite, and in such a case, the same effect as above can be obtained.
- the conversion catalyst body has carried on the zeolite by ion exchange of at least one transition metal of Cu, Zn and Fe, at least one of Pt, Pd, Rh and Ru Two noble metals may be supported, and in this case, the same effect as described above can be obtained.
- the reforming section 41 has a heating section 42 at a lower portion thereof, and the heating section 42 is connected to a combustion gas supply section 49 via a pipe.
- the reforming section 41 includes a raw material supply section 43 and a reformed water supply section 44. Is connected.
- the reforming section 41 is connected to a CO shift section 45, and the CO shift section 45 is connected to a CO purification section 47 via a pipe.
- Inside the CO shift section 45 the CO shift catalyst of the present invention is installed.
- a purified air supply unit 46 is connected to a pipe connecting the CO conversion unit 45 and the CO purification unit 47.
- the inlet of the fuel cell power generation unit 48 is connected to the CO purification unit 47 via a pipe.
- a combustion gas supply unit 49 is connected to an outlet of the fuel cell power generation system 48 via a pipe.
- the combustion gas supplied from the combustion gas supply unit 49 is heated by the heating unit 42 to heat the reforming unit 41.
- Water is supplied to the reforming section 41 from the reforming water supply section 44, and the water is heated by the heating section 42 to generate steam.
- the reformed gas is generated by heating the generated steam and the raw material gas supplied from the raw material supply unit 43 by the heating unit.
- the generated reformed gas is sent to the CO conversion unit 45, and the carbon monoxide contained in the reformed gas is reduced by the conversion reaction.
- the reformed gas with reduced carbon monoxide is sent to the CO purification section 47, where it is oxidized by the air supplied from the purified air supply section 46, thereby further reducing carbon monoxide. .
- the reformed gas that has exited the CO purification unit 47 is sent to the fuel cell power generation unit 48, where electricity is extracted by the generation of a power generation reaction.
- the reformed gas remaining without contributing to the power generation reaction in the fuel cell 48 is discharged from the outlet of the fuel cell 48, sent to the combustion gas supply unit 49 through a pipe, and is heated together with the combustion gas into the heating unit 4. Sent to 2.
- the carbon monoxide shift unit incorporated into the fuel cell power generation system of the present invention shown in Fig. 5 has improved durability of the CO shift catalyst, and is stable even when the device is repeatedly started and stopped. Can work on As a result, the CO concentration can be reduced at a high rate over a long period of time. Therefore, CO, which inhibits the electrochemical reaction between hydrogen and oxygen in the fuel cell, is stably removed by the CO purification unit, and a fuel cell power generation system that is effective for homes and vehicles can be realized.
- Noble metals (noble metal species are listed in the table) were supported on the Fe oxide by 2% by weight. Then, it was formed into a slurry, which was coated on a cordierite honeycomb, and placed in a shift conversion section 36 as a shift catalyst 37 shown in FIG.
- Methane gas is supplied from the raw material supply section 33 for 350 hours and water is supplied from the water supply section 34 for 1400 Z hours, and reforming is performed so that the temperature of the reforming catalyst 32 becomes 750 ° C.
- the heating amount was controlled in the heating section 35 to allow the steam reforming reaction to proceed.
- the conversion rate of methane becomes 100%
- the composition of the gas supplied to the metamorphic section 36 is approximately 8% by volume of carbon monoxide, 8% by volume of carbon dioxide, 20% by volume of water vapor, and the balance Became hydrogen.
- the gas composition discharged to the outlet of the shift section 36 was measured by gas chromatography.
- a composite oxide was prepared by calcining a precipitate formed by mixing 'Cr or Z and Ni nitrate with Fe nitrate (ratio is shown in the table). After supporting 2 wt% of Pt on the prepared composite oxide, the slurry was formed into a slurry, which was coated on a cordierite honeycomb, and placed in a metamorphic section 36 as a metamorphic contact medium 37 shown in FIG.
- Example 11 The operation was performed in the same manner as in Example 10, and the gas composition at the outlet of each of the shift sections 36 was measured by changing the temperature of the shift catalyst 37 as the initial characteristics of the shift catalyst 37. Thereafter, the temperature of the shift catalyst 37 was raised to 500 ° C. and cooled, and the same operation was performed again to measure the gas composition at the outlet of the shift section 36.
- the experimental results shown in Table 11 support the following facts described above.
- the initial activity is slightly lower than that of the Fe oxide alone by mixing the Fe oxide with the Cr or / and Ni oxide to form a composite oxide, but is 500.
- the activity after increasing to C is higher.
- the Fe oxide alone is exposed to high temperatures, it undergoes thermal degradation to lower its activity.However, by mixing Cr or Ni oxide into a composite oxide, the thermal degradation of the shift catalyst 37 Has been prevented.
- the experimental results shown in Table 12 support the following facts described above.
- the 7 nm and 2 m Fe oxide particles had higher CO concentrations than the other samples.
- the particle size of the Fe oxide is preferably from 10 nm to 1 ⁇ , and more preferably from 3 O nm to l // m.
- Example 2 The same operation as in Example 1 was performed for the operation, and the lowest value of the carbon monoxide concentration measured by changing the temperature of the shift catalyst 37 and the temperature of methane when the temperature of the shift catalyst 37 was 400 ° C. The concentration was measured. Table 13 shows the results of Samples 1 to 3.
- the experimental results shown in Table 14 support the following facts described above.
- the magnetic state of the Fe oxide is preferably ferromagnetic.
- Example 10 2% by weight of transition metal (Fe, Cu, Zn) supported on zeolite or A1, Ce, Ti oxide support by ion-exchange method, and noble metal (noble metal species are listed in the table) After loading 2% by weight of the catalyst, it was formed into a slurry, which was coated on a cordierite honeycomb and placed in a shift conversion section 36 as a shift catalyst body 37 shown in FIG. As in Example 10, the lowest value of carbon monoxide measured by changing the temperature of the shift catalyst 37 and the methane concentration when the temperature of the shift catalyst 37 was 400 ° C are shown in Table 15. Was. operation The operation was the same as in Example 10.
- the present invention can provide a hydrogen purifying apparatus that can be easily heated at the time of starting, for example, and has high C ⁇ purification efficiency.
- the present invention can provide a hydrogen purifier that can be easily heated at the time of start-up, prevents methanation, and increases the efficiency of the device.
Description
Claims
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US10/239,965 US7147680B2 (en) | 2001-01-26 | 2002-01-24 | Hydrogen purification apparatus and method and fuel cell power generation system and method |
EP02710339A EP1354853A4 (en) | 2001-01-26 | 2002-01-24 | HYDROGEN PURIFICATION DEVICE AND FUEL CELL POWER GENERATION SYSTEM |
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JP2001018997A JP2002226204A (ja) | 2001-01-26 | 2001-01-26 | 水素精製装置 |
JP2001-156069 | 2001-05-24 | ||
JP2001156069A JP2002348103A (ja) | 2001-05-24 | 2001-05-24 | 水素精製装置 |
JP2001176571A JP4867084B2 (ja) | 2001-06-12 | 2001-06-12 | 水素精製装置 |
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- 2002-01-24 CN CN200910160449A patent/CN101712461A/zh active Pending
- 2002-01-24 WO PCT/JP2002/000487 patent/WO2002059038A1/ja active Application Filing
- 2002-01-24 CN CN02800372A patent/CN1457320A/zh active Pending
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WO2004058399A2 (en) * | 2002-12-20 | 2004-07-15 | Honda Giken Kogyo Kabushiki Kaisha | Platinum and rhodium and/or iron containing catalyst formulations for hydrogen generation |
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CN1331730C (zh) * | 2006-01-12 | 2007-08-15 | 天津大学 | 富氢气体中co优先氧化的方法 |
Also Published As
Publication number | Publication date |
---|---|
US7147680B2 (en) | 2006-12-12 |
CN101712461A (zh) | 2010-05-26 |
US20030175562A1 (en) | 2003-09-18 |
EP1354853A1 (en) | 2003-10-22 |
EP1354853A4 (en) | 2009-08-19 |
CN1457320A (zh) | 2003-11-19 |
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