TW200812699A - A steam reforming catalyst, a device for producing hydrogen, and a fuel cell system - Google Patents

A steam reforming catalyst, a device for producing hydrogen, and a fuel cell system Download PDF

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TW200812699A
TW200812699A TW096123217A TW96123217A TW200812699A TW 200812699 A TW200812699 A TW 200812699A TW 096123217 A TW096123217 A TW 096123217A TW 96123217 A TW96123217 A TW 96123217A TW 200812699 A TW200812699 A TW 200812699A
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catalyst
steam reforming
rare earth
earth element
oxide
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TW096123217A
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Chinese (zh)
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TWI428177B (en
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Yasushi Hashimoto
Yasushi Satoh
Takaya Matsumoto
Yukihiro Sugiura
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Nippon Oil Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/63—Platinum group metals with rare earths or actinides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0205—Impregnation in several steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0207—Pretreatment of the support
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • 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
    • C01B3/40—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 characterised by the catalyst
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/58—Platinum group metals with alkali- or alkaline earth metals
    • B01J35/612—
    • B01J35/613—
    • B01J35/66—
    • 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
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
    • 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
    • C01B2203/06—Integration with other chemical processes
    • C01B2203/066—Integration with other chemical processes with fuel cells
    • 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
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • 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
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1082—Composition of support materials
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/14—Pore volume
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/16—Pore diameter
    • 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

Abstract

The present invention provides a steam reforming catalyst which can be used at a low pressure and a low steam/carbon ratio and is less in carbon deposition. The steam reforming catalyst comprises a support and ruthenium supported as an active metal thereon in an amount of 0.3 to 5 percent by mass on the basis of the support, the support being produced by supporting on α alumina with a pore volume of pore diameter of 50 nm or larger in the range of 0.2 to 1.0 ml/g, a rare earth element oxide in an amount of 2 to 25 percent by mass and an alkaline earth element oxide in an amount of 0.1 to 15 percent, on the basis of the α alumina.

Description

200812699 九、發明說明： 【發明所屬之技術領域】 觸ίί 蒸氣改質用觸媒，使用該水蒸氣改質用200812699 IX. Description of invention: [Technical field to which the invention pertains] Touching the catalyst for steam reforming, using the steam reforming

於氫製造製裎中，处女曰A 水b Η 重要地位者係使烴化合物類與 水療軋反應，以得到氫、一 所謂的經化合物類之水d:碳，等之 以被廣為利用，係因為相二==氣改質法之所 低價。 勹邳权於〇卩分乳化法等，其設備更為 =之水蒸氣改質用觸㈣㈣系為主（參照專利文獻 :、、而此等觸媒谷易發生碳析出，具有活性於短時間 ^牛山低的缺點。因此，大多以較高壓（2MPa以上）及高蒸 虱石厌比士（3.0口以上）進行運轉，但於燃料電池系統之情況 :’由裝置操作容易度而言，反應壓力係越低越佳，而由 舍電效率方面而言’蒸氣/碳比係越低越好。 另外’作為燃料電池之原料烴，由能量密度、經濟性、 操，容易度方面而言，較佳為煤油，但由於以上述鎳系觸 媒容易發生碳析出’故原料煙係限定於天然氣至石油腦程 度。 再者，作為觸媒載體-般係使用y氧化銘，但由於機械 強度並不疋那麼強’故於熱負荷較大之燃料電池的 DSS(Daily Start and Shutdown)運轉中觸媒將粉化，而 產生裝置差壓上升等問題。 312XP/發明說明書(補件)/96123217 5 200812699 作為機械強度較大之代表性的觸媒載體，可舉例如 化鋁’但習知使用α氧化鋁之水蒸氣改質用觸媒中係原 =石油腦㈣’碳析出抑制效果並不充分（ 獻2)。 丁〜又 專利文獻1:日本專利特開平4-363140號公報 專利文獻2 :日本專利特開平4-59048號公報 【發明内容】 ,本發明係提供低壓、低蒸氣/碳比且碳析出較少 命且機械強度較強之水蒸氣改質用觸媒，亦提供使用t 媒之氫製造裝置及燃料電池系統。 μ觸 本發明者等人針對烴之水蒸氣 碳質析出及提升機械強度的方法進行潛心研究， 現，藉由使用特定之水菽氣改晳 、、°果赉 者，遂完成本發明。貝用觸媒，則可同時達成兩 於=上本nt關於—種水蒸氣改質用觸媒’其特徵為 屬之舒而出 體為0·3〜5質量％載持作為活性金 屬之釘而成，·該载體係於隸5Gn 所曰〇/> X 相對於母《氧化鋁载持2〜25 貝置％之稀土類元素氧化物與〇.卜15質量％之驗土ζ i 氧化物而得。 貝里之鹼土類疋素 中，作為ΐΐίΓ關於上述記载之水蒸氣改質用觸媒，其 飾之1=^ 氧㈣’係使用選自H鋼及 種或2種以上的稀土類元素之氧化物。 外，本發明係闕於上述記载之水蒸氣改質用觸媒，其 312XP/發明說明書(補件)/96123217 6 200812699 I之！土類元素氧化物，係使用選自鎮，、銀及 ’’彳或2種以上的鹼土類元素之氧化物。 中另二tl"月係關於上述記载之水蒸氣改質用觸媒，其 中α虱化鋁之BET比表面積為3〜3〇mVg。 :Ϊ發明係關於氫製造裝置，其特徵為，使用上述 二IS巧氣改質用觸媒，藉由水蒸氣改質反應，自烴化 °物件到含有氫作為主成分之改質氣體。 :夕卜」：發明係關於一種燃料電池系統，其特徵為，具 有上述记載之氫製造裝置。 (發明效果） 所藉：：用本發明之水蒸氣改質用觸媒進行水蒸氣改 1真1成抑制碳質析出及提升機械強度。藉此，可達 使、疋地製造含有氫及—氧化碳之混合氣體，並可 使用作為燃料電池用燃料或其原料。 【實施方式】 以下，詳細說明本發明。 本發明之水蒸氣改質用觸媒’係於在特定之α氧化銘 、曰1定量載持稀土類元素氧化物及驗土類元素氧化物 ::、體上’以特定量載持作為活性金屬之釕而成者。 /觸媒載體成分’係使用孔徑5Gnm以上之具微孔的 '乳化鋁。孔# 50nm以上之細孔容積必須為 .ml/g於細孔容積小於〇.2ml/g時，觸媒活性將 不充足而不佳。另_十二 ,. 另方面，細孔容積大於1.0ml/g時，觸 媒強度將不足而不佳。 M2XP/發明說明書(補件)/96123217 Ί 200812699 另外，α氧化鋁之BET比表面積較佳為3~3〇mVg。在 BET比表面積小於3mVg時，觸媒活性將不充足而不佳。 在bet比表面積大於30mVg時，觸媒強度將不充足而 佳。 :為稀土類元素’較佳為使用選自銳、纪、鑭及飾之玉 ，2種以上之稀土類元素，更佳為鑭及鈽。 :媒載體中之稀土類元素的含量，係作為稀土類元素氧 ’相對於α氧化銘以外率（α氧化銘重量基準）計，必 =〜25質量％，較佳5〜2〇質量％ ’更佳ι〇〜ΐ5質量％。 在稀土類元素氧化物之含量多於25 、， 而出現於表面的金屬比例將極度減少，故不佳 :足質量％時，稀土類元素之碳析出抑制效果將 種土類元素，較佳為使用選自鎂、_、銷及鋇之1 或2種以上之驗土類金屬，更佳為鎂及銷。 :媒載體中之驗土類元素的含量，係作為 化物’相料α氧偏料率（ ^素乳 須為〇· 質封，較佳。.5〜12 基丰)计’必 在終+斗士 以貝里％，更佳1〜10質量％〇 双犬、7L素氧化物之含量多、t收 而出银你主r ,、 、1 3貝里/〇知，破集將增多 方面/、❸活性金屬比例將極度減少，故不佳.另-方面’在少於（M質量％時 * Μ ’另一 果及活性提升效果將不足而不佳。、、疋素之石反析出抑制效 本發明之觸媒中之釕的含詈， 持稀土類元f 糸相對於在α氧化鋁上載 素乳化物與驗土類元素氧化物而得之载體，以 312ΧΡ/發明說明書(補件)/96123217 8 200812699 外率（載體重量基準）計，作為舒原子， %，較佳1〜4質量％，更佳2〜3質量％ 、為〇.3〜5質量 質量％時，活性全屬之，隹竹、°在產了之含量多於5 例將極度減少，故不佳；另—古^出見於表面的金屬比 万面，在少於0 3暂旦0/。士 由於無法顯示充分之活性，故必須要大載觸里场’ 產生反應器必須增大為所需以上等問題。载持觸媒，而 2明之水蒸氣改質用觸媒之觸媒強度，較佳 法之觸媒壓壞強度為每觸媒粒為5 壞強度小於5⑽時’燃料電 觸㈣ 粉化，故不佳。 連轉中將务生觸媒破裂、 關於將稀土類元素及鹼土 方氺廿紅杜^ 頒70素载持於α氧化鋁上的 法亚無特別限制，可採用通常之含产 (porefilling)法等公知方米 ^ ' 八 、於妒认U 去通吊係使金屬鹽或錯合體 二:二Γ或丙_等之溶媒中，使其含浸於載體中。 踏、妒辦臨… 係適合使用氯化物、硝酸 ，凰 爪-夂皿、酉日酉夂鹽、乙醯乙酸鹽等。 浸關於载持步驟並無特職制，;料或逐次地進行含 特'藉由乾燥將水分大致地去除，此乾燥步驟亦無 疒义:適合使用於空氣下、惰性氣體下之溫度100〜150 轉如社乾秌步恥後’载持了稀土類元素及鹼土類元素之載 主、、乂係以350〜1 000 C之溫度進行燒成。在低於350°C的 月況’载持元素對载體的固定化將不足，而不佳。又，高 ;1000C %，由於發生載持元素之凝集，故不佳。燒成 312XP/發明說明書(補件)/96123217 9 200812699 環境氣體較佳為空氣下’於對氣體流量並 成時間較佳為2小時以上。在短於2小時的情：：制:燒 .兀素對載體的固定化將不足，而不佳。 载持 -將燒成之載體冷卻後，其次進行釕之载持。 :並無特別限制，可採用通常之含浸法:孔= 法。通常係使金屬鹽或錯合體溶解於水、乙、知方 溶媒中，使其含浸於載體中。所载持之全屬Γ^Γ等之 f體，係適合使用氯化物、确酸鹽、硫酸鹽；；：屬錯合 乙酸鹽等。載持次數亦無特別限制， 二=、乙醯 行含浸。 j -人或分為數次進In the production of hydrogen, the virgin 曰A water b Η is important for the reaction of hydrocarbon compounds with hydrothermal rolling to obtain hydrogen, a so-called compound-like water d: carbon, etc., which are widely used. It is because of the low price of phase two == gas reforming method.勹邳 〇卩 〇卩 〇卩 〇卩 乳化 乳化 乳化 , , , 其 其 其 其 其 其 其 其 其 乳化 乳化 乳化 乳化 乳化 乳化 乳化 乳化 乳化 乳化 乳化 乳化 乳化 乳化 乳化 乳化 乳化 乳化 乳化 乳化 乳化 乳化 乳化 乳化 乳化 乳化 乳化 乳化 乳化 乳化 乳化 乳化 乳化^The disadvantage of Niushan's low. Therefore, most of them operate at higher pressures (above 2 MPa) and high-distilled gangues (3.0 or more), but in the case of fuel cell systems: 'In terms of ease of operation, the reaction The lower the pressure system, the better, and the lower the vapor/carbon ratio is, the better the gas-fuel ratio is. In addition, as the raw material hydrocarbon of the fuel cell, in terms of energy density, economy, handling, and ease of use, Although kerosene is preferred, carbon deposition is likely to occur in the nickel-based catalyst. Therefore, the raw material smoke is limited to the natural gas to the petroleum brain. Further, as a catalyst carrier, y-oxidation is used, but due to mechanical strength Therefore, the catalyst will be pulverized during the DSS (Daily Start and Shutdown) operation of the fuel cell with a large heat load, and the differential pressure of the device will rise. 312XP/Invention Manual (Supplement)/96123217 5 200812699 as a machine A representative catalyst carrier having a large mechanical strength may be, for example, aluminum. However, it is conventionally known that the use of α-alumina for the reforming of water vapor to be used for the reforming of the original oil = petroleum brain (four) 'carbon precipitation suppression effect is insufficient ( 2) Patent Document 1: Japanese Laid-Open Patent Publication No. Hei-4-363140-A-Patent Publication No. JP-A No. 4-59048-A. The present invention provides a low pressure, a low vapor/carbon ratio and carbon. A catalyst for steam reforming which has a small amount of life and strong mechanical strength is also provided, and a hydrogen production device and a fuel cell system using a t medium are also provided. The inventors of the present invention have a carbonaceous carbon deposition and lifting machine for hydrocarbons. The strength method is studied intensively, and now, by using a specific water helium gas to modify, and the fruit is 赉, the 遂 遂 遂 。 。 贝 贝 贝 贝 贝 贝 贝 贝 贝 贝 贝 贝 贝 贝 贝 贝 贝 贝 贝 贝 贝 贝 贝 贝 贝 贝 贝 贝 贝 贝 贝The catalyst for steam reforming is characterized in that it is a genus of the genus and is contained in an amount of 0.3 to 5% by mass as a nail of the active metal. The carrier is attached to the 5Gn/> X relative to The mother "Alumina supports 2~25% of the rare earth element oxides and 1. 15% by mass of soil test ζ i oxide. In the alkaline earth glutinin of Berry, as a catalyst for steam reforming described above, it is decorated with 1=^ oxygen (four)' The oxide is selected from the group consisting of H steel and seed or two or more kinds of rare earth elements. The present invention is the catalyst for steam reforming described above, and the 312XP/invention specification (supplement)/96123217 6 200812699 I! The earth element oxide is an oxide of an alkaline earth element selected from the group consisting of town, silver, and ''彳 or two or more types. The other two tl" Catalyst, wherein the alpha bismuth aluminum has a BET specific surface area of 3 to 3 〇mVg. The invention relates to a hydrogen production apparatus characterized by using the above-mentioned two-IS catalyst for gas reforming, from a hydrocarbon reforming reaction to a reforming gas containing hydrogen as a main component. The invention relates to a fuel cell system characterized by comprising the hydrogen production apparatus described above. (Effect of the Invention) Borrowing: The steam reforming by the steam reforming catalyst of the present invention is carried out to suppress the carbonaceous precipitation and increase the mechanical strength. Thereby, a mixed gas containing hydrogen and carbon monoxide can be produced and used as a fuel cell fuel or a raw material thereof. [Embodiment] Hereinafter, the present invention will be described in detail. The catalyst for steam reforming of the present invention is based on the specific alpha oxide, 曰1 quantitatively carrying rare earth element oxides and soil-based element oxides::, on the body 'specifically carried as an activity The metal is the creator. The /catalyst carrier component 'is a microporous 'emulsified aluminum having a pore diameter of 5 Gnm or more. The pore volume of pore #50nm or more must be .ml/g. When the pore volume is less than ml.2ml/g, the catalytic activity will be insufficient. Another _12,. On the other hand, when the pore volume is greater than 1.0 ml/g, the catalyst strength will be insufficient. M2XP/Invention Manual (Supplement)/96123217 Ί 200812699 In addition, the BET specific surface area of α-alumina is preferably 3~3〇mVg. When the BET specific surface area is less than 3 mVg, the catalytic activity will be insufficient. When the bet specific surface area is larger than 30 mVg, the catalyst strength will be insufficient. The rare earth element is preferably a rare earth element selected from the group consisting of sharp, jade, enamel and jade, and more preferably two or more kinds of rare earth elements. The content of the rare earth element in the medium carrier is determined as the ratio of the rare earth element oxygen 'with respect to the α oxidation amount (the basis of the α oxidation weight), and is preferably 2 to 25% by mass, preferably 5 to 2% by mass. Better 〇 〇 ~ ΐ 5 mass%. When the content of the rare earth element oxide is more than 25, and the proportion of the metal present on the surface is extremely reduced, it is not preferable: when the mass is %, the carbon precipitation suppressing effect of the rare earth element is a soil type element, preferably It is more preferably magnesium and pin, using one or more types of earth-moving metals selected from the group consisting of magnesium, _, pin and strontium. : The content of soil-receiving elements in the medium carrier is the ratio of α-oxygen eccentricity of the material as a material (the yoghurt is 〇·mass seal, preferably. 5~12 kefeng) With Berry%, better 1~10% by mass, double dogs, 7L of oxides, and t, and silver, your main r, ,, 1 3 Berry / know, the collection will increase / The proportion of active metal in strontium will be extremely reduced, so it is not good. In other aspects, 'less than (M mass% * Μ 'the other fruit and activity enhancement effect will be insufficient.) The ruthenium containing ruthenium in the catalyst of the present invention holds the rare earth element f 糸 relative to the carrier obtained from the α-alumina-loading emulsifier and the soil-based elemental oxide, and the 312 ΧΡ/invention specification (supplement) /96123217 8 200812699 The external rate (carrier weight basis), as the Shu atom, %, preferably 1 to 4% by mass, more preferably 2 to 3% by mass, and 〇.3 to 5% by mass, the activity is all , 隹竹, ° in the production of more than 5 cases will be extremely reduced, it is not good; another - ancient ^ seen on the surface of the metal than the surface, less than 0 3 temporary 0 / Because the inability to display sufficient activity, it is necessary to have a large load to touch the field. The reactor must be increased to the required level. The catalyst is supported, and the catalyst strength of the catalyst for water vapor reforming is improved. The preferred method of catalytic crushing strength is 5 for each catalyst particle. When the bad strength is less than 5 (10), the fuel contact (four) is powdered, so it is not good. In the continuous transfer, the catalyst is broken, and the rare earth elements are Alkaline earth blushing red ^ 颁 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 70 To make a metal salt or a complex of two: diterpene or propylene, etc., soak it in a carrier. Steps, sputum, etc. Suitable for the use of chloride, nitric acid, phoenix-garnish, 酉日酉夂 salt , acetonitrile acetate, etc. There is no special system for the immersion step, and the material is continuously or repeatedly removed to remove the water by drying. This drying step is also meaningless: suitable for use under air, inert Under the gas, the temperature is 100~150, and after the company’s dryness, it carries the rare earth elements and The carrier of the earth element and the lanthanide are fired at a temperature of 350 to 1 000 C. At a temperature of less than 350 ° C, the carrier element will be insufficiently immobilized on the carrier, which is not good. High; 1000 C %, due to the agglomeration of the carrier element, it is not good. Firing 312XP / invention manual (supplement) / 96123217 9 200812699 The ambient gas is preferably under the air and the gas flow rate is preferably 2 More than an hour. In less than 2 hours:: system: burning. The immobilization of the carrier will be insufficient, which is not good. Carrier-cooling of the carrier after firing, followed by carrying the crucible. There is no particular limitation, and the usual impregnation method: hole = method can be used. Usually, the metal salt or the complex is dissolved in water, B, and a known solvent to be impregnated into the carrier. It is suitable for the use of chlorides, acid salts, and sulfates; it is a mismatched acetate. There is no special restriction on the number of carriers, and two = and 醯 are impregnated. j - person or divided into several times

載持後’藉由乾燥將水分A 特別限制，適合使用於空氣下、惰;驟亦無 〇C等。 月『汛體下之溫度100〜150 汝此所得之載持觸媒，視需要藉由 b 固定化處理以使1活性 仃延原處理和金屬 使用於處理方法並無特別限制，適人 ·/使用於U通下之氣相還原和液相還原。 通口 關:本發明之水蒸氣改質用觸媒之 制。例如可使#_形再 2別限 媒、加入適當黏結 Μ正粒成適虽乾圍的觸 等。或者，可使用於 形之觸媒、粉末狀觸媒 載體、擠㈣再f碎後整粒成適當範圍的 圓筒狀、片狀等適當::戈么形為球形、環狀、錠狀、 等，但由機械強戶之-等上經載持金屬的觸媒 又之觀點而言，較隹為诂 使用將觸媒本身成m 早仫為球形觸媒。又，可 ^為早塊體狀和蜂巢狀等之觸媒，或者 312XP/發明說明書(補件)/96123217 200812699 於使用了適當素材之單塊體和蜂巢等上塗敷觸媒者等。 作為使用於水蒸氣改質反應之反應器的形態，較佳係使 用流通式固定床反應器。關於反應器之形狀並無特別限 制，可使用圓筒狀、平板狀等配合各製程目的之公知的任 意形狀。又，亦可使用流動床反應器。 本發明中之水蒸氣改質反應，係指使烴化合物類於觸媒 存在下與蒸氣進行反應，轉換成含有一氧化碳及氫之重組 氣體（reforming gas)的反應。與蒸氣進行反應時，亦包 括伴隨著含氧氣體的情況（自發性熱重組反應）。 成為原料之烴化合物類，係碳數P40、較佳碳數卜如 之有機化合物。具體可舉例如飽和脂肪族烴、不飽和脂肪 族烴、芳香族烴等，又，關於飽和脂肪族烴 '不飽和^肪 族烴，可使用鏈狀、環狀之任一種。關於芳香族烴，亦可 任思使用單環、多環。此種烴化合物類可含有取代基。作 為取代基，可使用鏈狀、環狀之任—種，其例如有二基、 環燒基、芳基、烧芳基及芳烧基等。x，此等煙化合物土類 亦可藉由羥基、烷氧基、羥羰基、烷氧羰基、甲醯基之 含有雜原子之取代基予以取代。 本發明中可使用之烴化合物類的具體例，可舉例如 烧、乙烧、丙烧、丁燒、戊烧、己燒、庚燒、辛燒、 癸燒、十二烧、十三烧、十四烧、十五烧n儿 :席十八：、十九烧、二十烧等之飽和脂肪族烴：乙稀、 、丁~、戊烯、己烯等之不飽和㈣族烴；、 %己烷等之環狀烴；苯、甲苯、二甲关^ 不寻之方香族烴。 312ΧΡ/發明說明書(補件)/96123217 11 200812699 又亦可適田使用此等之混合物。可舉例如天然氣、哪、 石油腦、汽油、燈油、輕油等之工業上可低價取得之材料。 nt有含雜原子之取代基的烴化合物類的具體例， 可“列如曱酉子、乙醇、丙醇、丁醇、二甲基醇、酚 醚、乙醛、醋酸等。 另外，於上述原料亦可使用含有氫、水、二氧化碳、一 氧化碳等之原料。例如’於實施氫化脫硫作為原料前處理After the carrier, the moisture A is particularly limited by drying, and it is suitable for use in the air, inertia, and no 〇C. The temperature under the sputum is 100~150 汝 The carrier catalyst obtained by this method is not limited by the immobilization treatment of b as needed, so that the active tempering treatment and the metal treatment method are not particularly limited. Vapor phase reduction and liquid phase reduction under U pass. The port is a catalyst for the reforming of steam of the present invention. For example, it is possible to make the #_shape and then limit the medium, and add the appropriate bonding. Alternatively, it may be used in the form of a catalyst, a powdery catalyst carrier, a squeezing (four), and then smashing into a suitable range of a cylindrical shape, a sheet shape, etc.: a shape of a sphere, a ring, an ingot, Etc., but from the point of view of the mechanically strong households - the catalyst that carries the metal, the use of the catalyst itself is earlier than the spherical catalyst. Further, it is possible to use a catalyst such as an early block and a honeycomb, or a 312XP/invention specification (supplement)/96123217 200812699 to apply a catalyst to a monolith or a honeycomb using a suitable material. As a form of the reactor used for the steam reforming reaction, a flow-through fixed bed reactor is preferably used. The shape of the reactor is not particularly limited, and any shape known in the art for the purpose of each process can be used, such as a cylindrical shape or a flat plate shape. Also, a fluidized bed reactor can be used. The steam reforming reaction in the present invention refers to a reaction in which a hydrocarbon compound is reacted with steam in the presence of a catalyst to be converted into a reforming gas containing carbon monoxide and hydrogen. When reacting with steam, it also includes the case of an oxygen-containing gas (spontaneous thermal recombination reaction). The hydrocarbon compound to be a raw material is an organic compound having a carbon number of P40 and preferably a carbon number. Specific examples thereof include a saturated aliphatic hydrocarbon, an unsaturated aliphatic hydrocarbon, and an aromatic hydrocarbon. Further, as the saturated aliphatic hydrocarbon 'unsaturated aliphatic hydrocarbon, any of a chain and a ring may be used. Regarding aromatic hydrocarbons, it is also possible to use monocyclic or polycyclic rings. Such hydrocarbon compounds may contain a substituent. As the substituent, a chain or a ring may be used, and examples thereof include a diyl group, a cycloalkyl group, an aryl group, a calcined aryl group, and an aryl group. x, such a tobacco compound soil may also be substituted by a substituent containing a hetero atom of a hydroxyl group, an alkoxy group, a hydroxycarbonyl group, an alkoxycarbonyl group or a formazan group. Specific examples of the hydrocarbon compound which can be used in the present invention include, for example, calcination, ethyl bromide, propane calcination, butadiene calcination, pentylene calcination, calcination, heptane, cinnabar, teriyaki, twelfth burn, thirteen burn, Fourteen burning, fifteen burning n children: Xi 18:, nineteen burning, twenty burning and other saturated aliphatic hydrocarbons: ethylene, butyl, pentene, hexene and other unsaturated (qua) hydrocarbons; a cyclic hydrocarbon such as % hexane; a benzene, toluene, or dimethyl group; 312ΧΡ/Invention Manual (Repair)/96123217 11 200812699 It is also possible to use these mixtures. For example, natural gas, petroleum, petroleum, gasoline, kerosene, gas oil, and the like which are commercially available at low prices can be mentioned. Specific examples of the hydrocarbon compound having a substituent containing a hetero atom include "such as scorpion, ethanol, propanol, butanol, dimethyl alcohol, phenol ether, acetaldehyde, acetic acid, etc. Raw materials containing hydrogen, water, carbon dioxide, carbon monoxide, etc. may also be used as raw materials, for example, 'pretreatment with hydrodesulfurization as a raw material

之情況下，反應巾所使用之水的殘留部分並無特八 離，可直接使用。 刀 在使用作為原料之烴化合物中所含之硫濃度過高時 於有時將使本發明之改質觸媒不活性化，故其濃度係以斧 原子質量計，較佳為50質量ppb以下、更佳2〇 二 以下、再更佳質量ppb以下。心，若有必要 可於事先對原料進行脫硫。 供應至脫硫步驟之原料中的硫濃度並無特別限制，若 (於脫硫步驟中可轉換為上述硫濃度者則可予以使用。… 脫硫之方法亦無特別限制，可舉例如於適當觸媒與气之 存在下、，進行氫化脫硫，使所生成之硫化氯被氧化^吸 收之方法。作為可使用於此情況的觸媒之例子，可舉例如 以鎳-鉬、鈷-鉬等為成分之觸媒。另一方面，亦可二用^ 適當之收著劑的存在下，視需要於氫之共存下使硫 二 收著的方法。作為可使用於此情況的收著劑之例子 不如日本專利第2654515號公報、專利第268874g號公報 等所揭示之以銅-鋅為主成分之收著劑或以鎳_辞為主成 312XP/發明說明書(補件)/96123217 12 200812699 为之收著劑等。 質實:方法亦無特別限制，可藉由於水蒸氣改 應的之别一步設置脫 之脫硫製程中進行處理之煙亦可使用於獨立 统之觸媒的水蒸氣改質反應中’導入至反應系 數相對二:子定莫義 0 苗 數比（蒸氣/碳比）的值，較佳為 ==，!:5〜5、再更佳2〜3之範圍。於此值小於U 二’、上#易析出焦炭’或無法提升氫分率，另-方 【產二二的情況下，改質反應有進展，但有導致蒸 :。又備、療氣回收設備之大型化之虞。添加之方法並 热寸別限制，可與原料煙化合物類同時導人至反應區域， 亦可自反應器區域之各個位置或分為數次等而一部分一 部分地予以導入。 使用本發明之觸媒的水蒸氣改質反應中，導入至反應器 D之流通原料的空間速度，GHSV較佳為W iO OOOp、更佳 為50〜5,000h〗、再更佳為100〜LooohM之範圍。LHSV較 佳為0. 05〜5. Oh K更佳為〇.卜2. 〇h-i、再更佳為〇. 21. 〇[Γΐ 之範圍。 _ 反應溫度並無特別限定，較佳為200〜100(TC、更佳為 .3〇〇〜9〇〇C、再更佳為400〜800°C之範圍。 關於反應壓力亦無特別限定，較佳為大氣壓〜2〇MPa、更 佳為大氣壓〜5MPa、再更佳為大氣壓〜iMpa之範圍内實施， 視需要亦可於大氣壓以下進行實施。 312XP/發明說明書(補件)/96123217 13 200812699 以使用本發明之觸媒的水蒸氣改質反 ，碳與氫之混合氣體’若於固體氧化物：：：含有一 十月況下，料直接使料為燃料電池用之燃料^池般之 酸形燃料電池和固體高分、，、、又，於磷 化碳的情況下，可藉由並用一氧除-氧 作為燃料電池用氫的原料。 ，、少驟而適合使用 用其，為藉由使 :油等料)得到含有氫作為主成:之:質 置 明提供—賴料電池系統，係具有上述氫製造裝 圖1為表示本 以下，針對本發明之電池系統進行說明 發明之燃料電池系統之一例的模式圖。 f二’燃料槽3内之燃料係經由燃料泵4而流入至脫 =中。於脫硫器内可填充例如銅_辞系或鎳一鋅系之收 :二4。此時’若有必要可添加來自-氧化碳選擇氧化反 Η # 3氫氣體。於脫硫器5所脫硫之燃料係與自水 才曰1經由水泵2的水進行混合後，導人至氣化器6而被氣 化，送入至改質器7中。 使用本發明之觸媒作為改質器7之觸媒，填充至改質器 :改貝益反應官係藉由來自燃料槽之燃料及以陰極排出 氣（anode off gas)作為燃料之燃燒器18進行加溫，調節In this case, the residual portion of the water used in the reaction towel is not particularly detachable and can be used as it is. When the concentration of sulfur contained in the hydrocarbon compound used as the raw material is too high, the modified catalyst of the present invention may be inactivated. Therefore, the concentration is preferably 50 mass ppb or less based on the mass of the axe atom. More preferably 2〇2 or less, and even better quality ppb or less. The heart can be desulfurized in advance if necessary. The concentration of sulfur in the raw material supplied to the desulfurization step is not particularly limited. If it can be converted to the above sulfur concentration in the desulfurization step, the method of desulfurization is not particularly limited, and for example, In the presence of a catalyst and a gas, hydrogenation and desulfurization are carried out to oxidize and oxidize the produced sulfurized chlorine. Examples of the catalyst which can be used in this case include nickel-molybdenum and cobalt-molybdenum. The catalyst can be used as a component. On the other hand, it is also possible to use a suitable retracting agent in the presence of a suitable retracting agent to dilute sulfur in the presence of hydrogen as a retracting agent that can be used in this case. The example is not as disclosed in Japanese Patent No. 2654515, Patent No. 268874g, etc., which is mainly composed of copper-zinc-based retractor or nickel-based 312XP/invention specification (supplement)/96123217 12 200812699 For the purpose of receiving the agent, etc.. Quality: There is no special restriction on the method. The water can be used in the desulfurization process by the steam reforming process. 'Introduction to reaction coefficient in the reforming reaction For the second: the value of the seedling ratio (vapor/carbon ratio), preferably ==, !: 5~5, and even more preferably 2~3. The value is less than U2', upper #易析出焦炭' or can not increase the hydrogen fraction, the other side [in the case of the production of 22, the reforming reaction has progressed, but there are steaming:. Preparation, treatment of gas recovery equipment, the large-scale 虞. Add The method may be introduced into the reaction zone simultaneously with the raw material smoke compound, or may be introduced in part or in part from the various positions of the reactor zone, etc. The water vapor using the catalyst of the present invention. In the reforming reaction, the space velocity of the raw material to be introduced into the reactor D, the GHSV is preferably W iO OOOp, more preferably 50 to 5,000 h, and even more preferably 100 to Loooh M. The LHSV is preferably 0. 05~5. Oh K is better for 〇. Bu 2. 〇hi, more preferably 〇. 21. 〇[Γΐ范围。 _ The reaction temperature is not particularly limited, preferably 200~100 (TC, better) The range of .3 〇〇 to 9 〇〇C, more preferably 400 to 800 ° C. The reaction pressure is also not particularly limited, preferably atmospheric pressure ~ 2 〇 MPa More preferably, it is carried out in the range of atmospheric pressure to 5 MPa, more preferably atmospheric pressure to iMpa, and may be carried out under atmospheric pressure as needed. 312XP/Invention Manual (Supplement)/96123217 13 200812699 Water using the catalyst of the present invention Vapor reforming, a mixture of carbon and hydrogen 'If the solid oxide::: contains a month, the material is directly used as a fuel cell fuel cell-like acid fuel cell and solid high score, In the case of phosphating carbon, one oxygen de-iono-oxygen can be used in combination as a raw material for hydrogen for a fuel cell, and it is suitable for use in a small amount, and is obtained by using an oil or the like. The hydrogen-containing battery is provided as a main component: a battery cell system having the above-described hydrogen production device. Fig. 1 is a schematic view showing an example of a fuel cell system according to the invention of the battery system of the present invention. The fuel in the f' fuel tank 3 flows into the outlet through the fuel pump 4. The desulfurizer can be filled with, for example, copper _ _ _ or nickel-zinc series: two. At this time, if necessary, it is possible to add a selective oxidation reaction #3 hydrogen gas from the carbon oxide. The fuel desulfurized by the desulfurizer 5 is mixed with water from the water pump 2 via the water pump 2, and then introduced to the gasifier 6 to be vaporized and sent to the reformer 7. The catalyst of the present invention is used as a catalyst for the reformer 7, and is filled into the reformer: the fuel is recovered from the fuel tank by a fuel from the fuel tank and a burner 18 with a cathode off gas as a fuel. Warming, adjusting

為較佳200〜1 000。(：、更佳3〇〇〜9〇〇t：、再更佳400〜800°C 之範圍。 312XP/發明說明書(補件)/96123217 14 200812699 、晶古、:1戶:製造，含有氫與一氧化碳之改質氣體依序通 移反應器9、低溫轉移反應器1〇、一氧化碳選擇 乳化反應益1卜藉此使-氧化碳濃度減低至不致影塑到 燃料電池特性的程度。作為使 曰 Θ优用於此荨反應态之觸媒的例 …牛列如：於高溫轉移反應器9為鐵-鉻系觸媒；於 低溫轉移反應器1()為銅—辞季 ^ 、 ^ ^ 野乐哺媒，於一氧化碳選擇氧仆 反應為11為舒系觸媒等。 [實施例] 二=實施例更具體地說明本發明，但本發明並不 限疋於此專貫施例。 〈實施例1&gt; ⑴以細孔容積為0.4ml/g、表面積為 為觸媒載體A。 α乳化銘作 ⑵於觸媒载體Ajl，以載持氧化鈽量 %、載持氧化鎮量以外率計為5重 丰/為13貝置 3.- κ. 鈿盥础舻雜 $ X之里，含浸載持硝酸 飾與确H再以15Qt:乾燥 仃空氣燒成8小時。將此作為觸媒載體B。 ⑶於上述觸媒載體BJi ’以載持釕量 之量，含濘恭姓备 手0十為3貝I% 里各/又载持乳化舒，再以12(rc乾燥12 以5〇rc進行氫還原1小時。將此作為觸媒A。、後’ 〈實施例2&gt; 载持氧化鈣量設 將於實施例1中之硝酸鎂改為硝酸鈣、 為以外率計為5質量％者作成觸媒B。 〈實施例3&gt; 15 312XP/發明說明書(補件)/96123217 200812699 將於實施例1中之硝酸錢為賴鎖 為以外率計為5質量％者作成觸媒c。持减“置§又 〈實施例4&gt;It is preferably 200 to 1 000. (:, better 3〇〇~9〇〇t:, and even better range of 400~800°C. 312XP/invention manual (supplement)/96123217 14 200812699, Jingu,: 1 household: manufacturing, containing hydrogen The reforming gas with carbon monoxide is sequentially passed through the reactor 9, the low-temperature shift reactor, and the carbon monoxide selective emulsification reaction, thereby reducing the concentration of carbon monoxide to such an extent that it does not affect the characteristics of the fuel cell. An example of a catalyst that is excellent for use in this ruthenium reaction state is as follows: in the high temperature shift reactor 9 is an iron-chromium catalyst; in the low temperature shift reactor 1 () is a copper - rhyme ^, ^ ^ field In the case of Le Carnavide, the oxygen servant reaction is selected to be a sulphur catalyst or the like in the carbon monoxide. [Embodiment] The present invention is more specifically described in the following examples, but the present invention is not limited to this specific embodiment. Example 1&gt; (1) The pore volume was 0.4 ml/g, and the surface area was used as the catalyst carrier A. The α-emulsification was made (2) on the catalyst carrier Ajl, and the amount of ruthenium oxide supported and the amount of oxidized amount supported were measured. For 5 fengfeng/13 lbs. 3.- κ. 钿盥 舻 舻 X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X The gas is fired for 8 hours. This is used as the catalyst carrier B. (3) The above-mentioned catalyst carrier BJi' is used to carry the amount of ruthenium, and the amount of 泞 泞 备 备 备 0 0 0 0 0 0 0 0 0 0 0 0 0 Shu, and then hydrogen reduction by 12 (rc dry 12 at 5 rc for 1 hour. This is used as catalyst A., and then <Example 2> The amount of calcium oxide supported is set to be changed in the magnesium nitrate in Example 1. Catalyst B is used for calcium nitrate and 5% by mass of the external rate. <Example 3> 15 312XP/Invention Manual (Supplement)/96123217 200812699 The nitric acid in Example 1 is the rate of Lai lock. Calculated as 5% by mass of the catalyst c. Hold down "set § again <Example 4>

將於實施倒1中&gt; d ^ A _ 之文鎂改為硝酸鋇、载持#i介相旦π 為以外率計為5質量f乳化鋇1吕又 貝里％者作成觸媒D。 〈實施例5&gt; 將於實施例！中之確酸鈽改為确酸 ，為以外率計為13質_作成觸媒E。持平飞化―又 〈實施例6&gt; 將於實施例1中之硝酴 心月酉久鈽改為硝酸釔、載 為以外率計為13質量％去冼Λ、&amp; 戰得虱化釔罝设 貝里/°者作成觸媒F 〇 〈實施例7 &gt; 將於實施例1中之硝醅細 力酉夂錦改為硝酸鑭、載 為以外率計為13質量％ 戰符虱化鑭1权 貝里/〇者作成觸媒G。 〈比較例1&gt; (^將使用實施例1之觸媒载體A而去#杜* 土類元素，並以與實施例之而方未載=土類元素、驗 觸媒Η。 /直持載持舒者作為 〈比較例2&gt; 將於實施例1中之觸 (K 4nil/g、BET比表面積mmV 二，、細孔容積 &lt;比較例3&gt; g《r乳化銘者作成觸媒I。 將於實施例1中之載持氧化 媒j 〇 里口又為1貝者作成觸 312XP/發明說明書(補件)/96123217 16 200812699 〈比較例4&gt; 將於貫施例1中之载持氧化鎂量設為〇 〇8質量％者作 觸媒K。 〈水蒸氣改質反應〉In the implementation of the first 1 &gt; d ^ A _ the text of the magnesium changed to cerium nitrate, the carrier #i interfacial dan π for the external rate of 5 mass f emulsified 钡 1 Lu and Bailey% of the catalyst D. <Example 5> Will be an embodiment! In the middle of the acid sputum is changed to acid, for the external rate is 13 quality _ as a catalyst E. In the first embodiment, the niobium sputum in the first embodiment is changed to cerium nitrate, and the external rate is 13% by mass, and the war is deflated. Let Berry/° be used as a catalyst F 实施 <Example 7 &gt; The niobium fine 酉夂 酉夂 in Example 1 was changed to yttrium nitrate, and the external rate was 13% by mass. 1 right Berry / the leader made a catalyst G. <Comparative Example 1&gt; (^ The catalyst carrier A of Example 1 was used, and the #杜* earth element was used, and it was not carried out with the embodiment; the earth element and the test medium were held. The carrier was carried as <Comparative Example 2> The contact in Example 1 (K 4nil/g, BET specific surface area mmV II, pore volume &lt;Comparative Example 3&gt; g "r emulsified indicator as catalyst I" The carrier oxidizing agent j in the first embodiment will be made into a touch of 312XP/invention specification (supplement)/96123217 16 200812699 <Comparative Example 4> will be carried in the first embodiment When the amount of magnesium oxide is set to 8 mass%, it is used as catalyst K. <Water vapor reforming reaction>

一將上述觸媒以水蒸氣改質反應進行評價。反應係使用固 定床之微反應器。觸媒填充量為5Gcra3。使用脫硫燈油（密 度〇.793g/CIn3、硫分0.05質量卿）作為烴原料。反應條 件係:口下述。入口反應溫度5〇(rc、出口反應溫度·。c、 反應 £ 力 0. IMPa、热氣/碳比 &amp; 〇m〇1/m〇l、。 ,應氣體係使用氣體色層分析進行定量分析。將藉由反 μ 00小4後之生成氣體的組成所求得之原料轉化率示 於表1。於此，表1之轉化率係原料轉化為CO、CH4、C〇2 之比例，並以碳為基準而計算者。 定附著於 另外，反應結束後，自反應裝置取出觸媒並測 觸媒之碳量。結果示於表工。 〈觸媒壓壞強度〉 藉由任意抽出2〇個觸媒粒以 將上述觸媒之壓壞強度1田Μ抽出 木屋式測定法進行敎。將平均值示於表&quot; —上明顯可知’觸媒A〜G係相較於觸媒Η、 不者焦厌堆積量較少且較高之，員 係較觸媒！具有更高之機械強度。 X觸媒Η 〈實施例8 &gt; 統中，以燈油作為燃料 導入至改質器7之原料 、，於圖1所示之構成的燃料電池系 亚使用觸媒Α以進行試驗。此時， M2XP/發明說明書(補件)/%123217 200812699The above catalyst was evaluated by a steam reforming reaction. The reaction system uses a microreactor of a fixed bed. The catalyst loading is 5Gcra3. As the hydrocarbon raw material, a desulfurization lamp oil (density 793 793 g / C In3, sulfur content 0.05 mass) was used. The reaction conditions are as follows: The inlet reaction temperature is 5 〇 (rc, outlet reaction temperature ··c, reaction force 0. IMPa, hot gas/carbon ratio &amp; 〇m〇1/m〇l, ., gas system is quantified using gas chromatography The raw material conversion ratio obtained by the composition of the generated gas after the inverse 00 small 4 is shown in Table 1. Here, the conversion ratio of Table 1 is the ratio of the raw material converted to CO, CH4, C〇2, Based on the calculation of carbon, the catalyst is attached. After the reaction is completed, the catalyst is taken out from the reaction device and the amount of carbon in the catalyst is measured. The results are shown in the table. <Catalyst crush strength> By arbitrary extraction 2 One of the catalyst particles is subjected to the measurement of the crushing strength of the above-mentioned catalyst, and the average value is shown on the table. It is apparent that the catalyst A to the G system is compared with the catalyst. No, the amount of distraction is small and high, and the member is more catalytic! It has higher mechanical strength. X Catalyst 〈 <Example 8 &gt; In the system, the kerosene is used as fuel to be introduced into the reformer 7 The raw material and the fuel cell structure shown in Fig. 1 were tested using a catalyst cartridge. At this time, M2XP/invention description (S) / the 123,217,200,812,699%

氣體的蒸氣/碳比設定為3 〇。分析陰極入口之氣體，結 果為含有氫72容量％(水蒸氣除外）。 D 試驗期間（1 000小時）中，改質器均正 觸媒活性降低。燃料電池亦正常運作，二運作，未見到 利地運轉。 兒氣負荷15亦順The vapor/carbon ratio of the gas is set to 3 〇. The gas at the cathode inlet was analyzed, and the result was 72% by volume of hydrogen (except water vapor). During the D test (1 000 hours), the modifier has a reduced positive catalyst activity. The fuel cell also operated normally, and the second operation did not work well. Child's air load 15 is also smooth

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Sul sf 卜 ι zeCN196/01 -96/ffsi)_s^B&amp;餾/ΡΗΧΠ e 200812699 (產業上之可利用性） 藉由使用本發明之觸媒進行水蒸氣改質，則可 碳質析出及提升機械強度，並可長時間穩定地心制 及一氧化碳之混合氣體。 &lt;坆a有氧 【圖式簡單說明】 圖1為差壬士 g日+ 來、|_缔* λΟ»么μ 1 【主要元件符號說明】 1 水槽 2 水泵 3 燃料槽 4 燃料泵 5 脫硫 6 氣化器 7 改質器 8 空氣吹進器 9 高溫轉移反應器 10 低溫轉移反應器 11 一氧化碳選擇氧化反應器 12 陰極 13 陽極 14 固體高分子電解質 15 電氣負荷 16 排氣口 17 固體高分子形燃料電池 18 加溫用燃燒器 312ΧΡ/發明說明書(補件)/96-10/96123217 20Sul sf 卜 zeCN196/01 -96/ffsi)_s^B&amp; distillation/ΡΗΧΠ e 200812699 (industrial availability) By using the catalyst of the present invention for steam reforming, carbonaceous precipitation and upgrading Mechanical strength, and a stable mixture of carbon monoxide and carbon monoxide for a long time. &lt;坆a aerobic [Simple diagram of the diagram] Figure 1 is the difference gentleman g day + come, |_conclusion * λΟ» μ μ 1 [Main component symbol description] 1 sink 2 water pump 3 fuel tank 4 fuel pump 5 off Sulfur 6 gasifier 7 Reformer 8 Air insufflator 9 High temperature transfer reactor 10 Low temperature transfer reactor 11 Carbon monoxide selective oxidation reactor 12 Cathode 13 Anode 14 Solid polymer electrolyte 15 Electrical load 16 Exhaust port 17 Solid polymer Shape fuel cell 18 heating burner 312ΧΡ/invention specification (supplement)/96-10/96123217 20

Claims (1)

200812699 十、申請專利範園·· 1 · 一種水蒸氣改質用觸拔， 於葡辨在n Q c 4 、蜀媒其特被為於载體上，以相對 、—、' .〜5 i量％载持作為活性金屬之γ鄱 體係於孔徑5〇nra以卜夕“— 屬之舒而成，该載 化紹上，相容積為&quot;〜以心的α氧 ' 相對母α氧化鋁载持2〜25質量％之# 土,开夺 氧化物與0 1〜15晳旦0/々认， 貝里/。之稀土類兀素 〇 Α 貝里％之鹼土類元素氧化物而得。 2.如申請專利範圍第i 作為該稀土類元辛轰务…土 貝用觸媒，其中’ ^ #'❹選自銳、紀、鑭及飾之 1種或2種以上的稀土類元素之氧化物。 作明專利耗圍第1項之水蒸氣改質用觸媒，其中， ^^㈣素氧㈣’係使用選自鎂、舞、織鎖之 1種或2種以上的鹼土類元素之氧化物。 觸:广Π專利範圍第1至3項中任-項之水蒸氣改質用 觸媒’其中’ α氧化銘之BET比表面積為3〜3〇心。 5 -種氫製造裝置，其特徵為，使用中請專利範圍第1 項中任—項之水蒸氣改質_媒，藉由水1氣改質反 應’自烴化合物類得到含有氫作為主成分之改質氣體： 6.-種燃料電池系統’其特徵為’具有申請專利範圍 5項之氫製造裝置。 312ΧΡ/發明說明書(補件)/96-10/96123217 21200812699 X. Applying for a patented Fan Park····························································································· The amount of % carried by the γ 鄱 system as the active metal is obtained by the 孔径 “ — — — — — , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , Support 2~25% by mass of #土, open oxide and 0 1~15 旦旦0/々, Berry/. Rare earth 兀素〇Α Berry% alkali earth element oxide derived. 2. For example, the scope of patent application is i. The rare earth element is used as the catalyst for the rare earth element. The '^ #' is selected from the group consisting of one or more rare earth elements of sharp, kiln, enamel and decorative. Oxide. The catalyst for steam reforming in the first paragraph of the patent is used. Among them, ^^(tetra)oxine (4)' uses one or more kinds of alkaline earth elements selected from the group consisting of magnesium, dance and weaving. Oxide. Touch: The catalyst for steam reforming of any of the items in items 1 to 3 of the Guangqi patent range 'where' the BET specific surface area of the α-oxidation is 3~3〇. 5 - Hydrogen The apparatus is characterized in that, in use, the steam reforming medium of any one of the first paragraphs of the patent scope is used, and the reforming reaction of water 1 is used to obtain a reforming gas containing hydrogen as a main component from a hydrocarbon compound. : 6.----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
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JP5378148B2 (en) * 2009-10-22 2013-12-25 Ｊｘ日鉱日石エネルギー株式会社 Reforming catalyst, reformer, and hydrogen production device
JP2011088777A (en) * 2009-10-22 2011-05-06 Jx Nippon Oil & Energy Corp Hydrogen production apparatus and fuel cell system
JP2011088778A (en) * 2009-10-22 2011-05-06 Jx Nippon Oil & Energy Corp Hydrogen production apparatus and fuel cell system
JP2011210626A (en) * 2010-03-30 2011-10-20 Jx Nippon Oil & Energy Corp Fuel cell system
JP5409484B2 (en) * 2010-03-30 2014-02-05 Ｊｘ日鉱日石エネルギー株式会社 Steam reforming catalyst, hydrogen production apparatus and fuel cell system
JP2011210634A (en) * 2010-03-30 2011-10-20 Jx Nippon Oil & Energy Corp Fuel cell system
JP5351089B2 (en) * 2010-03-30 2013-11-27 Ｊｘ日鉱日石エネルギー株式会社 Steam reforming catalyst, hydrogen production apparatus and fuel cell system
JP5603120B2 (en) * 2010-03-30 2014-10-08 Ｊｘ日鉱日石エネルギー株式会社 Steam reforming catalyst, hydrogen production apparatus and fuel cell system
JP5462685B2 (en) * 2010-03-30 2014-04-02 Ｊｘ日鉱日石エネルギー株式会社 Steam reforming catalyst, hydrogen production apparatus and fuel cell system
KR102080819B1 (en) * 2011-11-21 2020-02-24 사우디 아라비안 오일 컴퍼니 Method and a system for combined hydrogen and electricity production using petroleum fuels
CN102872867B (en) * 2012-10-19 2014-05-07 厦门大学 Catalyst used for hydrogen production by methanol steam reforming and preparation method of catalyst
JP6541339B2 (en) * 2014-12-01 2019-07-10 クラリアント・プロドゥクテ・（ドイチュラント）・ゲゼルシャフト・ミト・ベシュレンクテル・ハフツング Steam reforming catalyst for hydrocarbon-containing gas, hydrogen production apparatus, and hydrogen production method
CN104617318B (en) * 2015-01-07 2016-08-24 浙江大学 Double turbine co-generation unit based on aluminum-water reaction and method
JP2016165664A (en) * 2015-03-09 2016-09-15 学校法人 工学院大学 STEAM MODIFICATION CATALYST HAVING Ru ON CARRIER CONTAINING 12SrO 7Al2O3 COMPOUND HAVING MAYENITE STRUCTURE, PREFERABLY CARRIER MAINLY CONTAINING THE COMPOUND
CN107537590B (en) * 2016-06-28 2020-07-10 中国石油化工股份有限公司 Low-purity hydrogen reduction method for hydrocarbon steam conversion catalyst
CN109718864B (en) * 2017-10-31 2022-02-08 中国石油化工股份有限公司 Catalyst carrier, supported catalyst, preparation method and application of supported catalyst, and method for preparing hydrogen by reforming methane steam
CN108408689B (en) * 2018-05-30 2021-08-17 大连大学 Anhydrous hydrogen production system
CN114471643B (en) * 2020-10-27 2023-09-01 中国石油化工股份有限公司 Catalyst for hydrogen production and preparation method and application thereof
CN115305123B (en) * 2022-07-27 2023-10-27 中钢设备有限公司 Method and device for directly purifying and reducing coke oven gas in DRI preheating process

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0683787B2 (en) * 1990-06-19 1994-10-26 財団法人石油産業活性化センター Catalyst for steam reforming
JP3226558B2 (en) * 1991-03-12 2001-11-05 日石三菱株式会社 Catalyst for high temperature steam reforming of hydrocarbons
JP3717219B2 (en) * 1995-12-21 2005-11-16 株式会社コスモ総合研究所 Method for producing highly dispersed steam reforming catalyst and method for producing hydrogen
WO1999028027A1 (en) 1996-11-28 1999-06-10 Idemitsu Kosan Co., Ltd. Alumina-supported ruthenium catalyst
KR100825157B1 (en) 2000-11-08 2008-04-24 이데미쓰 고산 가부시키가이샤 Catalyst for hydrocarbon reforming and method of reforming hydrocarbon with the same
JP4648566B2 (en) 2001-05-11 2011-03-09 Ｊｘ日鉱日石エネルギー株式会社 Autothermal reforming catalyst and method for producing fuel gas for fuel cell

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