WO2001064337A1 - Procede de preparation d'un catalyseur utilise pour retirer le co d'un gaz contenant de l'hydrogene - Google Patents

Procede de preparation d'un catalyseur utilise pour retirer le co d'un gaz contenant de l'hydrogene Download PDF

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Publication number
WO2001064337A1
WO2001064337A1 PCT/JP2001/001689 JP0101689W WO0164337A1 WO 2001064337 A1 WO2001064337 A1 WO 2001064337A1 JP 0101689 W JP0101689 W JP 0101689W WO 0164337 A1 WO0164337 A1 WO 0164337A1
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WIPO (PCT)
Prior art keywords
catalyst
hydrogen
containing gas
alumina
reaction
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PCT/JP2001/001689
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English (en)
Japanese (ja)
Inventor
Takashi Umeki
Kozo Takatsu
Tetsuya Fukunaga
Satoshi Nakai
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Idemitsu Kosan Co., Ltd.
Osawa, Mitsuru
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Priority claimed from JP2000058559A external-priority patent/JP4478281B2/ja
Priority claimed from JP2000058558A external-priority patent/JP4478280B2/ja
Priority claimed from JP2000152483A external-priority patent/JP5164297B2/ja
Priority claimed from JP2000263199A external-priority patent/JP4620230B2/ja
Application filed by Idemitsu Kosan Co., Ltd., Osawa, Mitsuru filed Critical Idemitsu Kosan Co., Ltd.
Priority to AU2001236090A priority Critical patent/AU2001236090A1/en
Publication of WO2001064337A1 publication Critical patent/WO2001064337A1/fr

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    • 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
    • H01M8/0662—Treatment of gaseous reactants or gaseous residues, e.g. cleaning
    • 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
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/462—Ruthenium
    • 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
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
    • C01B3/58—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids including a catalytic reaction
    • C01B3/583—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids including a catalytic reaction the reaction being the selective oxidation of carbon monoxide
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
    • C10K3/02—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment
    • C10K3/04—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment reducing the carbon monoxide content, e.g. water-gas shift [WGS]
    • 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
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0435—Catalytic purification
    • C01B2203/044—Selective oxidation of carbon monoxide
    • 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
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/047—Composition of the impurity the impurity being carbon monoxide
    • 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

Definitions

  • the present invention relates to a method for producing a C 0 removal catalyst in a hydrogen-containing gas, a C 0 removal catalyst produced by the production method, and a method for removing C 0 in a hydrogen-containing gas using the catalyst.
  • the hydrogen-containing gas is useful as a hydrogen-containing gas for a fuel cell.
  • pure hydrogen is preferable as a fuel for such a fuel cell using a platinum-based electrode catalyst, but from a practical point of view, it is inexpensive and has excellent storage properties, or a complete public supply system is already available.
  • Various fuels eg, methane or natural gas (LNG), propane, butane, etc., petroleum gas (pG), naphtha, gasoline, kerosene, gas oil, etc.
  • Alcohol-based fuels such as tanol
  • a CO oxidation catalyst is conventionally, P t / alumina, P t / S N_ ⁇ 2, P t / C, C o T i Oz, Popukarai bets, which catalyst system which P dZ alumina are known
  • these catalysts do not have sufficient resistance to humidity, have a low and narrow reaction temperature range, and have low selectivity for CO oxidation, so that a large amount of hydrogen such as reformed gas is present.
  • a large amount of hydrogen must be sacrificed by oxidation in order to reduce the small amount of C ⁇ to a low concentration of less than 10 ppm by volume.
  • Japanese Patent Application Laid-Open No. 5-2017702 discloses a method for selectively removing C 0 from a hydrogen-enriched C 0 -containing gas and supplying the same to a fuel cell system for automobiles. A manufacturing method is disclosed.
  • the catalyst a carrier in which Rh or Ru is supported on an alumina carrier is used, but there is a problem that it can be applied only to a low C0 concentration, and there is also room for improvement in the catalytic activity at low temperatures. Is left.
  • ruthenium used for a ruthenium-based catalyst is a noble metal
  • a catalyst used as a supporting component is generally expensive. Therefore, in order to make a catalyst containing a ruthenium component industrially useful, it is necessary to reduce not only the catalyst performance but also the catalyst price.
  • the above-mentioned conventional ruthenium-based catalyst has a practically insufficient catalytic activity per supported ruthenium, and a more active catalyst has been desired.
  • the present invention has been made in view of the above, and provides a catalyst for removing C0 from a hydrogen-containing gas having improved catalytic activity, a method for producing the same, and a method for removing C0 from a hydrogen-containing gas using the catalyst. It is for this purpose.
  • the present inventors have assiduously studied and found that the object of the present invention can be effectively achieved by supporting ruthenium on a refractory inorganic oxide carrier, thereby completing the present invention.
  • the present invention uses a nitrate compound as a ruthenium compound, supports it on a refractory inorganic oxide carrier, dries it, reduces it without firing, and reduces
  • alumina having a pore distribution as a carrier
  • the ruthenium component is dispersed relatively uniformly in the carrier, but the ruthenium component that contributes to the reaction during the reaction is only the one existing near the outer surface of the carrier. And the ruthenium component present inside Did not contribute to the reaction, and found that ruthenium, which is an active component in the carrier, was distributed more on the outer surface side of the carrier. It was found that it could be used as a CO removal catalyst for its purpose. In addition, it has been found that by performing C0 removal treatment using the catalyst obtained by the above method, a hydrogen-containing gas suitably applicable to a fuel cell can be efficiently obtained.
  • the gist of the present invention resides in a method for producing a C0 removal catalyst in a hydrogen-containing gas in which ruthenium is supported on a refractory inorganic oxide carrier.
  • Ruthenium nitrate (a) is supported on a refractory inorganic oxide carrier, dried and reduced without firing, which is a catalyst for removing CO from hydrogen-containing gas. Production method,
  • a cross section of the catalyst is unidirectionally converted to ruthenium atoms using an electron probe microanalysis (EPMA) device.
  • EPMA electron probe microanalysis
  • the ruthenium nitrate (a) is supported on a refractory inorganic oxide carrier, dried, and calcined without firing. Removal catalyst.
  • FIG. 1 is a cross-sectional view of an example of the C ⁇ oxidation catalyst of the present invention, and a diagram showing the relationship between the distance in the width direction and the X-ray intensity.
  • the method for producing a catalyst for removing C ⁇ in a hydrogen-containing gas comprises supporting ruthenium on a refractory inorganic oxide carrier, and in particular, converting ruthenium nitrate (a) into a refractory inorganic oxide 'carrier. It is characterized in that it is reduced after being supported on a carrier and dried without firing, and is further characterized by using alumina or alumina-titania as a carrier, the carrier containing an active metal or a compound in a hydrogen-containing gas carrying a compound.
  • alumina having a maximum value of the pore distribution within a pore radius of 100 A or less. Characterized by
  • Examples of the refractory inorganic oxide carrier used in the present invention include a porous carrier made of alumina, titaure, silica, zirconia, or the like, or a material containing two or more of these. Among them, those composed of alumina and alumina-titaure are preferred. It is sufficient that the raw material of the alumina of the above carrier contains aluminum atoms. Examples of those usually used include aluminum nitrate, aluminum hydroxide, aluminum alkoxide, pseudo-boiling aluminum, ⁇ -alumina, and a-alumina. Pseudo-boehmite alumina, ⁇ -alumina, ⁇ -alumina, etc. can be made from aluminum nitrate, aluminum hydroxide, aluminum alkoxide, and the like.
  • the titania raw material of the above carrier may be any material containing a titan atom, but usually, titanium alkoxide, titan tetrachloride, amorphous titania powder, anata type titania powder, rutile Mold titer powder and the like.
  • Amorphous titania powder, anatase-type titania powder, rutile-type titania powder, and the like can be made from titanium alkoxide, titanium tetrachloride, and the like.
  • any material containing a silicon atom may be used, but silicon tetrachloride, sodium silicate, ethyl silicate, silica gel, silica sol, and the like can be used.
  • Silica gel can be made from silicon tetrachloride, sodium silicate, ethyl silicate, silica sol, and the like.
  • any material containing a zirconium atom may be used, but zirconium hydroxide, zirconium oxychloride, zirconium oxynitrate, zirconium nitrate, zirconium tetrachloride and zirconium powder can be used.
  • Zircoure powder is hydroxyl
  • the refractory inorganic oxide carrier which can be made of zirconium oxide, zirconium oxychloride, zirconium oxynitrate, zirconium nitrate, or zirconium tetrachloride, can be produced from the above-mentioned raw materials by a known method.
  • any method can be used for producing the alumina-titania carrier, as long as a carrier comprising both of them can be produced.
  • the method of adhering titania to the surface is suitably used.
  • a method of mixing titania and aluminum there is a method of mixing titania powder and alumina powder or pseudo-boehmite alumina with water, followed by molding, drying and firing. Extrusion may be usually used for molding, and at that time, an organic binder can be added to improve moldability.
  • a suitable carrier can also be obtained by mixing titania with an alumina binder. In this case, it is preferable that the mass ratio of the obtained chidair / alumina is 10/90 to 90/10.
  • the method of adhering titania to the alumina compact may be as follows. Add and disperse the titania powder and, if necessary, the organic binder and pseudo-boehmite alumina powder in the organic solvent. The alumina compact is immersed in this mixed liquid (usually in a slurry form), and the mixed liquid is sufficiently immersed. After the titania powder is adhered to the alumina compact, the alumina compact is taken out. What is necessary is just to dry and bake this alumina compact.
  • titanium alkoxide or titanium tetrachloride and an aluminum molded body are added to alcohol, and water is added to this solution to hydrolyze titanium alkoxide or titanium tetrachloride, and the aluminum molded body is formed on the aluminum molded body. Is dried and calcined. Is also good.
  • titania may be attached in such a manner that titania is supported on the alumina molded body. In the case of a method in which titania is adhered to an alumina molded body, the obtained titania / alumina mass ratio is 0.199.99 to 50/50, preferably 0.5 / 99.5 to 5. 0/50, more preferably 1/99 to 50/50.
  • the titania / alumina mass ratio is 0.1 / 99.99 to 90/10, preferably 0.5 / 99.95 to 90/10, and more preferably 199. 9 0/10.
  • alumina and titania used in the method for producing the alumina-titania carrier, the same materials as those described above are used.
  • the alumina used for the above-mentioned alumina or alumina-titania carrier preferably has a maximum pore distribution value with a pore radius of 100 or less.
  • alumina having a maximum value of the pore distribution at a location exceeding the pore radius of 100 A is used, the catalytic activity at low temperatures may be reduced. More preferably, alumina having a maximum value of the pore distribution at a pore radius of 60 or less may be used.
  • pseudo-boehmite alumina is used as a raw material for alumina, the carrier changes into low alumina during preparation (after calcination) of the support, and the pore distribution thereof is measured and determined.
  • the pore distribution mentioned above is determined by the N 2 adsorption method, BJH in (B arrett - - J oyner H a 1 enda) present invention is obtained by analyzing with method, the above carriers, the active metal compound
  • a compound may be supported by a ruthenium compound (a) or a ruthenium compound (a) and an alkali metal compound and / or alkaline earth metal. And the like metal compounds (b).
  • a catalyst preparation solution obtained by dissolving a salt in water, ethanol, or the like is used.
  • a ruthenium nitrate [eg, Ru (N 03) 3 ] is used in terms of catalytic activity.
  • the support treatment on the carrier may be performed by the usual impregnation method, coprecipitation method or competitive adsorption method using the catalyst preparation liquid.
  • the treatment conditions are not particularly limited, but usually, the carrier may be brought into contact with the catalyst preparation solution at room temperature to 90 ° C for 1 minute to 10 hours.
  • the ruthenium component is unevenly distributed on the outer surface side. I can do it.
  • the amount of the component (a) to be carried is not particularly limited, but is usually preferably from 0.05 to 10% by mass, more preferably from 0.3 to 3% by mass, as ruthenium metal relative to the carrier. is there. If the amount of the ruthenium is too small, the conversion activity of C0 may be insufficient.If the amount is too large, the conversion activity of C0 corresponding to the amount of ruthenium cannot be obtained, which is economically disadvantageous. In some cases.
  • the support After supporting the ruthenium compound on the support, the support is dried.
  • a drying method for example, natural drying, a rotary evaporator, a blow dryer may be used for 0.5 to 24 hours at 50 to 200 ° C.
  • it after drying, it can be calcined at 350 to 550 ° (: further at 380 to 550, for 2 to 6 hours, further 2 to 4 hours.
  • ruthenium nitrate is used as the compound, it must be subjected to reduction without firing.
  • alkali metal potassium, cesium, rubidium, sodium, and lithium are preferably used.
  • K 2 for example, K 2 ,,. Shed 16, KB r, ⁇ ⁇ ⁇ 0, KCN, ⁇ C 0 3, KC 1, ⁇ C 1 0 3, ⁇ C 1 0, KF, ⁇ ⁇ C 0, ⁇ ⁇ F, ⁇ ⁇ 2 ⁇ 0 4, ⁇ ⁇ 5 (P 0 4) 2, KH S_ ⁇ 4, KI, KI ⁇ 3, KI 0 4, K 4 I 0, ⁇ ⁇ , ⁇ ⁇ 0 2, ⁇ ⁇ 0, Kappa_ ⁇ _Ita, kappa [rho F 6 , ⁇ 3 ⁇
  • norium, calcium, magnesium, and strontium are preferably used.
  • B a salt 2 such as; C a B r 2, C a I 2, C a C l 2, C a (C 1 0 3 ) 2 , C a (IO
  • the component (b) may be supported by a usual impregnation method, a coprecipitation method, or a competitive adsorption method using the catalyst preparation liquid.
  • the treatment conditions are not particularly limited, but usually, the carrier may be brought into contact with the catalyst preparation solution at room temperature to 90 ° C. for 1 minute to 10 hours.
  • the amount of the component (b) to be carried is not particularly limited, but is generally preferably from 0.01 to 10% by mass as a metal relative to the carrier, and most preferably from 0.03 to 3% by mass. . If the amount is too small, the selective oxidation activity of CO may be insufficient, and if it is too large, the selective oxidation activity of CO will be insufficient and the amount of metal used will be unnecessarily excessive. The catalyst cost may increase.
  • the carrier After supporting the component (b) on the carrier, the carrier is dried.
  • a drying method for example, air drying, a rotary evaporator, or a blow dryer may be used. After drying, baking can be carried out usually at 350 to 550 ° C, further at 380 to 550 ° C, for 2 to 6 hours, and further for 2 to 4 hours.
  • the components (a) and (b) may be loaded separately, but they are loaded at the same time because they have higher catalytic activity and are economically advantageous. In the present invention, it is important that the powder is subjected to reduction without drying or firing, if necessary, after firing. In the case where the component (b) is first supported, the component (a) may be subjected to a supporting process after drying, and then, if necessary, a firing step may be performed after each drying.
  • the shape and size of the catalyst prepared in this way examples thereof include powder, spherical, granular, honeycomb, foam, fibrous, cloth, plate, and ring.
  • Various commonly used shapes and structures, such as shapes, can be used.
  • the catalyst itself may be formed by extrusion or the like, or a method of attaching the catalyst to a substrate such as a honeycomb ring may be used, and the method is not particularly limited.
  • '-The present invention also provides a CO oxidation catalyst comprising at least a ruthenium component supported on an inorganic refractory carrier, wherein a cross section of the catalyst is obtained by using an electron probe / microanalysis (EPMA) device.
  • EPMA electron probe / microanalysis
  • FIG. 1 shows a cross-sectional view of an example of the above catalyst and the relationship between the distance in the width direction and the X-ray intensity.
  • the carrier has a spherical or columnar shape. Therefore, r (distance from the center to the catalyst surface) in the present invention refers to the radius when the support is spherical, and refers to the radius of the cross section cut parallel to the bottom surface when the support is cylindrical.
  • Spherical and cylindrical shapes include not only strictly spherical and cylindrical shapes but also those which can be regarded as substantially spherical and cylindrical although some of the shapes are deformed.
  • the ruthenium distribution of the present invention can be achieved by preparing a catalyst in a carrier having a shape other than the spherical and cylindrical shapes according to the above-mentioned spherical and cylindrical shapes.
  • the diameter of the above-mentioned C0 oxidation catalyst or the diameter of the above-mentioned cross section is preferably from 1 to 1 Omm, and more preferably from 2 to 6 mm. If the diameter of the catalyst is smaller than the above range, the effect of supporting the outer surface is not sufficient, and if it is larger than the above range, the catalytic activity may not be sufficient and may not be preferable.
  • Hydrogen reduction is usually carried out under a stream of hydrogen at a temperature of 450-550 ° C, preferably 480-530 ° C, for 1-5 hours, preferably 1-2 hours. Do.
  • the method for oxidizing and removing C ⁇ of the present invention mainly comprises hydrogen obtained by reforming or partially oxidizing a raw material for hydrogen production that can be converted into a hydrogen-containing gas by a reforming reaction and a partial oxidation reaction. It is suitably used to selectively remove C 0 in gas (hereinafter also referred to as reformed gas, etc.) and is used to produce hydrogen-containing gas for fuel cells, but is not limited to this. Absent.
  • the step for obtaining the reformed gas or the like can be performed by any method such as a conventional hydrogen production step, particularly a method implemented or proposed in a hydrogen production step in a fuel cell system. it can. Therefore, in a fuel cell system provided with a reformer or the like in advance, the reformed gas may be prepared by using the reformer as it is.
  • Hydrocarbons that can be used to produce hydrogen-rich gas by steam reforming and partial oxidation as raw materials for hydrogen production, for example, hydrocarbons such as methane, ethane, propane, and butane. Hydrogen or natural gas (LNG), naphtha, gasoline, kerosene, light oil, heavy oil, hydrocarbons such as asphalt, alcohols such as methanol, ethanol, propanol, butanol, methyl formate, Oxygenated compounds such as methyl tertiary butyl ether (MTBE) and dimethyl ether, as well as various city gases, LPG, synthesis gas, and coal can be used as appropriate.
  • LNG Hydrogen or natural gas
  • MTBE methyl tertiary butyl ether
  • dimethyl ether as well as various city gases, LPG, synthesis gas, and coal can be used as appropriate.
  • what kind of raw material for hydrogen production should be used should be determined in consideration of various conditions such as the scale of the fuel cell system and the supply situation of the raw material, but usually, methanol and methane are also used. Alternatively, LNG, propane or LPG, naphtha or lower saturated hydrocarbon, city gas, etc. are suitably used.
  • the desulfurization method is not particularly limited, hydrodesulfurization, adsorption desulfurization and the like can be used as appropriate.
  • reforming reaction Technologies belonging to reforming or partial oxidation (hereinafter also referred to as reforming reaction, etc.) include steam reforming, partial oxidation, combined steam reforming and partial oxidation, autothermal reforming, and others. Such as reforming reactions.
  • steam reforming steam reforming
  • partial oxidation or other reforming reactions for example, thermal reforming reactions such as thermal decomposition
  • catalytic reforming reactions such as catalytic decomposition shift reaction, etc.
  • a steam reforming reaction is generally an endothermic reaction, so a steam reforming reaction and a partial oxidation may be combined (automatic reforming) to compensate for this endothermic component, are possible various combinations, such as previously by utilizing the shift reaction is reduced by converting a part in advance in the C 0 2 and H 2 is reacted with H 2 0 to C_ ⁇ to live
  • steam Reforming can also be performed.
  • the heat generated by the partial oxidation can be used as it is for steam reforming, which is an endothermic reaction.
  • the raw material is hydrogen-containing gas of the present invention, hereinafter the same
  • reformed gas due to said reaction into contains a large amount in addition to C 0 2 and unreacted steam, etc. and some C ⁇ hydrogen
  • the effective catalyst for the reforming reaction is the type of raw material (fuel) and the reaction.
  • a wide variety are known according to the type of the compound or the reaction conditions. Specific examples of some of them include catalysts that are effective for steam reforming of hydrocarbons, methanol, and the like.
  • Cu—Zn0-based catalysts Cu—Cr 2 0-based catalyst, supported Ni-based catalyst, Cu—Ni—Zn0-based catalyst, Cu—Ni—MgO-based catalyst, Pd—Zn0-based catalyst, and the like.
  • the catalyst effective for the catalytic reforming reaction and partial oxidation of hydrocarbons include a supported Pt-based catalyst, a supported Ni-based catalyst, and a supported Ru-based catalyst.
  • the reformer There is no particular limitation on the reformer, and any type of reformer, such as those commonly used in conventional fuel cell systems, can be applied, but many reforming reactions such as steam reforming reaction and decomposition reaction are endothermic.
  • the reaction is a reaction
  • a reaction device or a reactor heat exchanger type reaction device or the like having a good heat supply property
  • examples of such a reactor include a multitubular reactor, a plate-fin reactor, and the like.
  • the heat supply method include heating using a burner, a method using a heating medium, and a partial heating method. There is heating by catalytic combustion using oxidation, and the like, but is not limited thereto.
  • the reaction conditions for the reforming reaction vary depending on the raw materials used, the reforming reaction, the catalyst, the type of the reaction apparatus, the reaction system, and other conditions, and may be appropriately determined.
  • the conditions should be such that the conversion of the feedstock (fuel) is sufficiently high (preferably to 100% or close to 100%) and the hydrogen yield is as high as possible. It is desirable to select one. If necessary, a method of separating and recycling unreacted hydrocarbons and alcohols may be adopted. If necessary, generated or unreacted C 0 and water may be appropriately removed.
  • the hydrogen content is high, and hydrocarbons and alcohols To obtain a desired reformed gas in which raw material components other than hydrogen such as hydrogen are sufficiently reduced.
  • the present invention it is intended to be C 0 2 by selectively oxidizing the C 0 by adding oxygen to the source gas (reformed gas) containing C ⁇ a small amount as a main component, hydrogen Oxidation must be minimized. Further, generation or, (because in the feed gas hydrogen is present, there is a possibility that the reverse shift reaction occurs.) C 0 conversion reaction to 2 of CO was present in the feed gas this both to suppress is necessary. Since the catalyst according to the present invention is usually used in a reduced state, it is preferable to perform a reduction operation with hydrogen or the like when not in a reduced state. With this catalyst,
  • C 0 course and this show good results against 2 content of less raw material gas to the selective oxidation removal of C ⁇ , good results can be obtained even with C 0 2 content is more conditions.
  • the reformed gas of a typical C 0 2 concentration in the fuel cell system or the like i.e., C ⁇ 2 5 to 3 3 volume%, preferred properly 1 0-2 5 volume%, more preferred properly 1 Gas containing 5 to 20% by volume is used.
  • steam is usually present in the raw material gas obtained by steam reforming, etc., but the lower the steam concentration in the raw material gas, the better.
  • 5 to 3 0 capacity 0/0 If this degree has been included degree problem is not the name o
  • the C 0 concentration in the raw material gas having a low C 0 concentration (0.6% by volume or less) can be effectively reduced, and the CO concentration is relatively high (0.6 to 2.6%). (0% by volume) C 0 in the source gas can also be suitably reduced.
  • the temperature is 60 to 300 ° C. In this temperature range, the selective conversion and removal of C ⁇ can be performed efficiently.
  • the conversion and removal reaction of C 0 is an exothermic reaction like the oxidation reaction of hydrogen, which occurs at the same time, and the recovery of the generated heat and utilization in the fuel cell improves the power generation efficiency. Is effective.
  • oxygen gas When adding oxygen gas to the reformed gas or the like, usually, pure oxygen (0 2), air or oxygen-enriched air is preferably used.
  • the addition amount of the oxygen gas is suitably adjusted so that ⁇ 2 / C 0 (molar ratio) is preferably 0.5 to 5, and more preferably 1 to 4. If this ratio is too small, the removal rate of C0 will be low, and if it is too large, the consumption of hydrogen will be too high, which is not preferred.
  • the reaction pressure is not particularly limited, but in the case of a fuel cell, the reaction is usually carried out within a pressure range from normal pressure to IMPa (Gauge), preferably from normal pressure to 0.5 MPa (Gauge). If the reaction pressure is set too high, it is economically disadvantageous because it is necessary to increase the power for the pressure increase, and in particular, if the reaction pressure exceeds IMP a (Gauge), the regulation of the High Pressure Gas Control Law will be imposed. In addition, there is a problem that the safety is reduced because the explosion limit is widened.
  • the reaction is generally carried out in a very wide temperature range of 60 ° C. or more, preferably 60 to 300 ° C., while maintaining the selectivity to the C 0 conversion reaction stably. Can be performed at any time. If the reaction temperature is lower than 60 ° C, the reaction rate becomes slow, so that the CO removal rate (conversion rate) tends to be insufficient within the practical range of GHSV (gas volume space velocity).
  • the reaction is suitably carried out by selecting the normal, the GHSV to 5, 0 0 0-1 0 0 0 0 range hr 1.
  • the GHSV is reduced, a large amount of catalyst is required, while the GHSV is reduced. Larger values decrease the CO removal rate.
  • it is selected in the range of 6,000 to 600,000 hr '. Since the C • conversion reaction in the CO conversion removal process is an exothermic reaction, the reaction raises the temperature of the catalyst layer. If the temperature of the catalyst layer is too high, the selectivity of the catalyst for C ⁇ conversion is usually deteriorated. For this reason, it is not preferable to react a large amount of C 0 on a small amount of catalyst in a short time. For this reason, it may be better not to make GHSV too large.
  • the reactor used for the conversion and removal of C ⁇ is not particularly limited, and various types can be used as long as the above reaction conditions can be satisfied, but this conversion reaction is an exothermic reaction. Therefore, in order to facilitate temperature control, it is desirable to use a reactor or a reactor having good removability of reaction heat.
  • a heat exchange type reactor such as a multi-tube type or a plate-fin type reactor is suitably used.
  • a method of circulating the cooling medium in the catalyst layer or flowing the cooling medium outside the catalyst layer can be adopted.
  • JP-A-3-9362 and JP-A-11-86892 disclose a method of contacting a Ru / a-alumina catalyst with a hydrogen gas containing CO. It has been disclosed. However, when hydrogen gas contains carbon dioxide, a methane conversion reaction of carbon dioxide, which is a side reaction, also occurs, and hydrogen is consumed correspondingly, which is not desirable. Therefore, the development of a catalyst with high selectivity for the main reaction of CO methane conversion is desired. Was.
  • the step of removing C ⁇ by the methanation reaction is the same as the catalyst used as the above-mentioned catalyst for selective oxidation and removal of C ⁇ , that is, the nitrate (a) ′ of ruthenium is applied to the refractory inorganic oxide carrier. It is possible to use a reduced catalyst without drying after the supporting treatment and calcination.
  • the catalyst is a catalyst for removing carbon monoxide in a hydrogen-containing gas having a high selectivity in a metathesis reaction of carbon monoxide, which is a main reaction.
  • the removal of C ⁇ by the methanation reaction can be carried out under almost the same conditions as the reaction conditions in the above-mentioned selective oxidation removal step of C ⁇ , but the reaction temperature is usually 100 to 350 °. C, preferably, in a very wide temperature range of 150 to 300 ° C., it can be suitably carried out while maintaining the selectivity of C 0 to the methane reaction stably. If the reaction temperature is lower than 100 t, the reaction rate becomes slow. Therefore, the CO removal rate (conversion rate) tends to be insufficient within a practical range of GH SV (gas space velocity). On the other hand, when the temperature exceeds 350 ° C., the selectivity decreases, that is, C 02 becomes more likely to form a methanation, which is not preferable.
  • a C0 selective oxidation removal step may be performed before or after the removal step.
  • P t / alumina, P t / S n 0 2 , P t / C, C o / T i 02, P d / alumina, R UZ alumina, the R u- K / alumina can be used.
  • the reaction conditions normally temperature 6 0 ⁇ 3 0 0 ° C, pressure atmospheric pressure ⁇ IMP a (G auge), 0 2 / CO ( molar ratio) 0.
  • the hydrogen-containing gas produced according to the present invention by adopting the range of 0 to 100,000 hr 1 is as described above.
  • the C ⁇ concentration is sufficiently reduced, the poisoning and deterioration of the platinum electrode catalyst of the fuel cell can be sufficiently reduced, and the life and power generation efficiency-power generation performance can be greatly improved. It is also possible to recover the heat generated by this CO conversion reaction.
  • the CO concentration in the hydrogen-containing gas containing a relatively high concentration of C ⁇ can be sufficiently reduced.
  • the hydrogen-containing gas obtained by the present invention can be suitably used as a fuel for various hydrogen-oxygen fuel cells, and in particular, platinum (platinum) is used for at least the fuel electrode (negative electrode).
  • platinum platinum
  • Fuel to various types of hydrogen-oxygen fuel cells such as phosphoric acid fuel cells, KOH fuel cells, and solid polymer fuel cells, etc. It can be used advantageously.
  • the C0 removal catalyst in a hydrogen-containing gas with improved catalytic activity can be produced.
  • Catalyst 2 was obtained in the same manner as in Example 1, except that the alumina was changed to one having a maximum value of the pore distribution in 29 pore radii.
  • the supported amount of ⁇ 1 was 1.0% by mass (based on the carrier).
  • Ruthenium nitrate aqueous solution (Ru content: 50 g / liter) 2 cc was added with water so that the water absorption of the alumina carrier as a whole was obtained to obtain an impregnation liquid. Then, after impregnating the impregnating solution with 10 g of the alumina powder having a pore distribution maximum value in a pore radius of 19 persons and drying at 120 ° C. for 2 hours, 500 ° C. Calcination was performed for 4 hours at C to obtain Catalyst 4. The supported amount of 811 was 1.0% by mass (based on the carrier).
  • Catalyst 5 was obtained in the same manner as in Example 4, except that j-alumina was changed to one having a maximum value of the pore distribution at a pore radius of 29.
  • the supported amount of 1 ⁇ 1 was 1.0.0% by mass (based on the carrier).
  • Catalyst 6 was obtained in the same manner as in Example 4, except that alumina was changed to one having a maximum value of the pore distribution in 200 pore radii. .
  • the supported amount of 1 ⁇ 11 was 1.0% by mass (based on the carrier).
  • Ruthenium chloride (hydrate) (Ru content: 39.15% by mass) 0.2554 g was dissolved in water equivalent to the amount of water absorbed by the alumina carrier to obtain an impregnating liquid.
  • 10 g of alumina powder having a pore distribution maximum value in a pore radius of 19 persons was impregnated with the above impregnating liquid, dried at 120 ° C for 2 hours, and then dried at 500 ° C. After calcining for 4 hours, catalyst 8 was obtained.
  • the supported amount of R ⁇ was 1.0% by mass (based on the carrier).
  • Catalyst 9 was obtained in the same manner as in Example 1, except that ⁇ -alumina was changed to one having a maximum value of the pore distribution in 200 pore radii.
  • the supported amount of Ru was 1.0% by mass (based on the carrier).
  • a catalyst 10 was obtained in the same manner as in Example 7, except that the iron alumina was changed to one having a maximum value of the pore distribution for 200 pore radii.
  • the loading of 1 to 11 was 1.0% by mass (based on the carrier)
  • Rutile type titania powder (Ishihara Sangyo Co., Ltd., CR_EL) 160 g and pseudo-boehmite alumina powder (Catalyst Chemical Co., Ltd., Cata 10 id -AP) 59.7 g was mixed well in a beaker and then put into a kneader. Ion-exchanged water was added thereto, and the mixture was sufficiently kneaded and heated to adjust the water content to an appropriate hardness for extrusion. This was formed into a cylindrical shape having a diameter of 2 mm using an extruder, dried at 120 ° C. for 24 hours, and subsequently baked at 500 ° (: 24 hours. Toalumina was converted to iron alumina, and had a maximum value of the pore distribution at a pore radius of 25 A. The mass ratio of titania / alumina in this molded product was 80/20.
  • Ruthenium chloride (Ru content: 38.03% by mass) was dissolved in 0.263 g of water and 0.026 g of potassium nitrate to form a mixed solution. This impregnating liquid was impregnated into 10 g of the above molded product, and dried at 60 ° C. for 12 hours. This was calcined at 500 ° C. for 4 hours to obtain catalyst 11.
  • the supported amount of Ru was 1.0% by mass (based on the carrier), and the supported amount of ⁇ was 0.1% by mass (based on the carrier).
  • Catalyst 12 was prepared in the same manner as in Example 9 except that the pseudo-boehmite alumina powder was changed to a-alumina powder having a pore distribution maximum value at a pore radius of 45 A and the amount was also changed to 40 g. Prepared.
  • the supported amount of Ru was 1.0% by mass (based on the carrier), and the supported amount of K was 0.1% by mass (based on the carrier).
  • the S value of the catalyst obtained in each of the following examples and the C The degree was measured by the following method.
  • Hydrogen-containing gas A C 0/0 / C 0 2 / H 0 / N / H
  • Ruthenium nitrate (Ru (NO 3 )) aqueous solution 50 g / liter as Ru metal 2 Milliliters are transferred to a 50-milliliter beaker, and ion exchanged water 1 .6 Milliliters were added and stirred until uniform.
  • alumina support KHD24 manufactured by Sumitomo Chemical Co., Ltd., spherical shape having a diameter of 2 to 4 mm.
  • the ruthenium nitrate aqueous solution prepared above was added dropwise to the alumina carrier while thoroughly stirring the carrier with a glass rod, and the mixture was further thoroughly stirred for about 1 minute. Then, the mixture was allowed to stand at room temperature for 3 hours, then placed in a drier, and dried at 120 ° C. for 24 hours to obtain a catalyst 13 having Ru supported on an alumina carrier at 1.0% by weight.
  • Rutile titania (T i 0 2, Ishihara Sangyo Kaisha Ltd., CR- EL, one surface area: 7 m2 / g) 1 6 0 g and pseudo Bemai Toarumi Na powder (Catalysts & Chemicals Industries Co., Ltd., C ata 1 0 id-AP) 59.7 g was mixed and sufficiently kneaded with ion exchange water in a kneader under heating to adjust the water content to an extent suitable for extrusion molding. This was extruded into a cylindrical shape with a diameter of 2 mm and a length of 0.5 to 1 cm using an extruder, and dried at 120 ° (: 24 hours) with a dryer. The mixture was calcined at 0 ° (: 4 hours to obtain a titania / alumina carrier. The weight ratio of titania / alumina was 80/20.
  • Ruthenium chloride (RuC1a ⁇ nH20, Ru metal content ': 38.0 3% by weight) Weigh 0.263 g into a beaker. This placed the nitrate force re um (KN 0 3) 0. 2 5 9 g, was further added and dissolved Ion exchange water 1 ml.
  • Example 12 the carrier was a ruthenium-containing or urea-containing solution. , And 1% by weight of Ru and 0.1% by weight of K were loaded on the titania / alumina carrier in the same manner as in Example 12 except that the mixture was left at room temperature for 3 hours before being put into a dryer. Catalyst 15 was obtained. Table 2
  • Catalysts were prepared in the same manner as in each of Examples 1 to 3, and Examples 11 to 14 were performed using the catalysts in the following manner.
  • Each catalyst was prepared in 16 to 32 mesh, and the microreactor was filled with 1 cc of the catalyst, and reacted under the following conditions.
  • Table 3 shows the concentration of C ⁇ at the outlet of the reactor (volume, p pm), the concentration of methane at the outlet (volume, p pm), and the selectivity of the C ⁇ methanation reaction (%).
  • C 0 methanation reaction selectivity (%) [(inlet C concentration (volume ppm) one outlet CO concentration (volume ppm)) / (outlet CH 4 concentration (volume ppm)] X 100
  • H 2 0 (2 0 volume 0/0), H 2 ( 6 4 5 volume 0/0.)
  • GHSV 8 , 0 0 0 hr
  • the present invention relates to a method for producing a catalyst for removing C 0 from a hydrogen-containing gas, a catalyst for removing C 0 from a hydrogen-containing gas produced by the production method, and a method for removing C 0 from a hydrogen-containing gas using the catalyst.
  • the hydrogen-containing gas is useful as a hydrogen-containing gas for a fuel cell.

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Abstract

L'invention concerne un procédé de préparation d'un catalyseur utilisé pour retirer le CO d'un gaz contenant de l'hydrogène, dans lequel un composé métallique actif tel que le nitrate de ruthénium est déposé sur un support d'oxyde non organique réfractaire tel que l'alumine et l'alumine-titane. Ce catalyseur constitué d'un support et du composé actif qui y est déposé, est séché, puis réduit sans combustion, ou peut être constitué d'alumine présentant une valeur maximale de répartition de pores fins se trouvant dans la plage de diamètre de pore égale ou inférieure à 100 Å: L'invention concerne également un catalyseur préparé à l'aide de ce procédé, ledit catalyseur possédant une activité de catalyseur significativement améliorée.
PCT/JP2001/001689 2000-03-03 2001-03-05 Procede de preparation d'un catalyseur utilise pour retirer le co d'un gaz contenant de l'hydrogene WO2001064337A1 (fr)

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JP2000058559A JP4478281B2 (ja) 2000-03-03 2000-03-03 水素含有ガス中のｃｏ除去触媒の製造方法、及びその製造方法で製造された触媒、並びに該触媒を用いる水素含有ガス中のｃｏの除去方法
JP2000058558A JP4478280B2 (ja) 2000-03-03 2000-03-03 水素含有ガス中のｃｏ除去触媒の製造方法、及びその製造方法で製造された触媒、並びに該触媒を用いる水素含有ガス中のｃｏの除去方法
JP2000-58559 2000-03-03
JP2000-58558 2000-03-03
JP2000-152483 2000-05-24
JP2000152483A JP5164297B2 (ja) 2000-05-24 2000-05-24 Ｃｏ酸化触媒及び水素含有ガスの製造方法
JP2000-263199 2000-08-31
JP2000263199A JP4620230B2 (ja) 2000-08-31 2000-08-31 水素含有ガス中の一酸化炭素除去触媒及び該触媒を用いる水素含有ガス中の一酸化炭素の除去方法

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Cited By (3)

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Publication number Priority date Publication date Assignee Title
WO2008075761A1 (fr) * 2006-12-20 2008-06-26 Nippon Oil Corporation Catalyseur conçu pour réduire la concentration en monoxyde de carbone
WO2010113381A1 (fr) 2009-03-31 2010-10-07 新日本石油株式会社 Procédé de production d'un catalyseur utilisé dans une réaction d'oxydation sélective du monoxyde de carbone
CN103203236A (zh) * 2013-04-03 2013-07-17 北京三聚创洁科技发展有限公司 一种有机硫加氢催化剂及其制备和使用方法

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JPH0393602A (ja) * 1989-09-07 1991-04-18 Asahi Chem Ind Co Ltd 一酸化炭素の選択的除去方法
JPH07256112A (ja) * 1994-03-19 1995-10-09 Masahiro Watanabe 改質ガス酸化触媒及び該触媒を用いた改質ガス中一酸化炭素の酸化方法
JPH11102719A (ja) * 1997-09-26 1999-04-13 Toyota Motor Corp 一酸化炭素濃度低減装置および一酸化炭素濃度低減方法並びに一酸化炭素選択酸化触媒
JP2001017861A (ja) * 1999-07-05 2001-01-23 Tanaka Kikinzoku Kogyo Kk 改質ガス中の一酸化炭素の選択酸化触媒

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Publication number Priority date Publication date Assignee Title
JPH0393602A (ja) * 1989-09-07 1991-04-18 Asahi Chem Ind Co Ltd 一酸化炭素の選択的除去方法
JPH07256112A (ja) * 1994-03-19 1995-10-09 Masahiro Watanabe 改質ガス酸化触媒及び該触媒を用いた改質ガス中一酸化炭素の酸化方法
JPH11102719A (ja) * 1997-09-26 1999-04-13 Toyota Motor Corp 一酸化炭素濃度低減装置および一酸化炭素濃度低減方法並びに一酸化炭素選択酸化触媒
JP2001017861A (ja) * 1999-07-05 2001-01-23 Tanaka Kikinzoku Kogyo Kk 改質ガス中の一酸化炭素の選択酸化触媒

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008075761A1 (fr) * 2006-12-20 2008-06-26 Nippon Oil Corporation Catalyseur conçu pour réduire la concentration en monoxyde de carbone
JPWO2008075761A1 (ja) * 2006-12-20 2010-04-15 新日本石油株式会社 一酸化炭素濃度を低減するための触媒
US8093178B2 (en) 2006-12-20 2012-01-10 Nippon Oil Corporation Catalyst for reducing carbon monoxide concentration
WO2010113381A1 (fr) 2009-03-31 2010-10-07 新日本石油株式会社 Procédé de production d'un catalyseur utilisé dans une réaction d'oxydation sélective du monoxyde de carbone
JP2010234257A (ja) * 2009-03-31 2010-10-21 Jx Nippon Oil & Energy Corp 一酸化炭素の選択的酸化反応用触媒の製造方法
US8349762B2 (en) 2009-03-31 2013-01-08 Jx Nippon Oil & Energy Corporation Method for producing catalyst for use in preferential oxidation reaction of carbon monoxide
CN103203236A (zh) * 2013-04-03 2013-07-17 北京三聚创洁科技发展有限公司 一种有机硫加氢催化剂及其制备和使用方法

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