WO2016047504A1 - Composition de catalyseur de reformage à la vapeur et catalyseur de reformage à la vapeur - Google Patents

Composition de catalyseur de reformage à la vapeur et catalyseur de reformage à la vapeur Download PDF

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WO2016047504A1
WO2016047504A1 PCT/JP2015/076168 JP2015076168W WO2016047504A1 WO 2016047504 A1 WO2016047504 A1 WO 2016047504A1 JP 2015076168 W JP2015076168 W JP 2015076168W WO 2016047504 A1 WO2016047504 A1 WO 2016047504A1
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steam reforming
reforming catalyst
catalyst
particles
catalyst composition
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PCT/JP2015/076168
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English (en)
Japanese (ja)
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憲之 高橋
林　克彦
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三井金属鉱業株式会社
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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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/847—Vanadium, niobium or tantalum or polonium
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the present invention relates to a steam reforming catalyst composition and a steam reforming catalyst composition comprising a steam reforming catalyst active component having a function capable of promoting a steam reforming reaction to obtain hydrogen by reforming a fuel gas containing hydrocarbon. It relates to a reforming catalyst.
  • a fuel cell is a cell that converts chemical energy into electrical energy by electrochemically reacting hydrogen and oxygen, and as the hydrogen source, hydrogen obtained by reforming city gas, hydrocarbons, etc. It's being used.
  • the city gas is a gaseous fuel mainly composed of natural gas, and typically contains 87 vol% or more of methane.
  • a nickel-based catalyst having a transition metal element represented by nickel as a catalytically active component is known.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2005-74396
  • Cu, Co, Fe, Ni, Mn, Zn, Sn, Cd, Pd Cu, Co, Fe, Ni, Mn, Zn, Sn, Cd, Pd, and the like as metal particle dispersed oxides that can function as catalysts for steam reforming.
  • “Reducible metal oxides” that can be reduced to metal under hydrogen atmosphere from room temperature to 1500 ° C., such as oxides of Ag, Ru, Rh, Mo, W and In; Al, Mg, Si, Zr, Ti, Hf And oxide particles such as oxides of Ce, etc., which are composed of a solid phase with a “non-reducible metal oxide” that is not reduced to metal under a hydrogen atmosphere at room temperature to 1500 ° C.
  • a metal particle dispersed oxide is disclosed, in which metal particles are deposited and internal metal particles are deposited inside the oxide particles.
  • Patent Document 2 Japanese Patent Application Laid-Open No. 2005-144402 discloses, as a steam reforming catalyst capable of suppressing coking (carbon deposition), a catalyst activity comprising fine particles of a metal selected from iron group metals such as nickel.
  • a steam reforming catalyst having a core-shell type structure in which the component is a core and the core is surrounded by a shell comprising a catalyst support component selected from silica, alumina, zirconia and titania.
  • transition metal-based catalyst in which a transition metal element represented by nickel is used as a steam reforming catalyst active component, it has been necessary to further improve the steam reforming performance.
  • this kind of transition metal catalyst in order to use this kind of transition metal catalyst as a steam reforming catalyst, it is necessary to reduce and activate it before using it.
  • this type of catalyst is reduced at a temperature of 500 ° C. or higher, the phase transition of the oxide to the metal phase causes sintering (sintering), so the activity of the active component of the steam reforming catalyst decreases.
  • sintering sintering
  • the present invention is superior in steam reforming performance to conventionally proposed transition metal catalysts comprising a transition metal element as a steam reforming catalyst active component, and further, reduction treatment at a temperature of 500 ° C. or higher And, in the reforming reaction, it is intended to propose a new steam reforming catalyst composition in which the catalyst performance does not decrease.
  • the present invention proposes a steam reforming catalyst composition containing catalytically active particles containing a steam reforming catalyst active component and vanadium.
  • the steam reforming catalyst composition proposed by the present invention is superior in steam reforming performance to the conventionally proposed transition metal catalysts by containing vanadium and is reduced at a temperature of 500 ° C. or more. It is also possible to suppress the deterioration of the catalyst performance by suppressing the sintering during the treatment or the reforming reaction.
  • FIG. 2 It is the block diagram which showed the outline of the fuel-reforming evaluation apparatus used by the gas-reforming evaluation test of the Example. It is a FE-SEM / EDX image of the steam reforming catalyst composition (sample) obtained in Example 2-1, (a) is an enlarged photograph (SEM image) of catalytically active particles, (b) in the particles It is an enlarged photograph showing the distribution of oxygen (O), (c) an enlarged photograph showing the distribution of vanadium (V) in the particle, and (d) shows the distribution of nickel in the particle It is an enlarged picture. Note that “Grey”, “K” and “L” at the upper left of FIG. 2 relate to the observation conditions and are not related to the present invention.
  • K and L are symbols of characteristic X-rays used for element detection, and indicate the orbits (energy levels) of the excited electrons. It is a XRD pattern of the steam reforming catalyst composition (sample before gas evaluation test, referred to as "pre") obtained in Example 1, Examples 2-1 to 2-3 and Comparative Example 1. It is a XRD pattern of the steam reforming catalyst composition (sample before gas evaluation test, referred to as "pre") obtained in Examples 2-4 to 2-7. It is a XRD pattern of the steam reforming catalyst composition (sample after gas evaluation test, referred to as "aged”) obtained in Example 1, Examples 2-1 to 2-3 and Comparative Example 1.
  • Example 2-7 It is a SEM image of the steam reforming catalyst composition (sample after gas evaluation test, referred to as "aged”) obtained in Example 2-3. It is a SEM image of the steam reforming catalyst composition (sample after gas evaluation test, referred to as “aged”) obtained in Example 2-4. It is a SEM image of the steam reforming catalyst composition (sample after gas evaluation test, referred to as “aged”) obtained in Example 2-5. It is a SEM image of the steam reforming catalyst composition (sample after gas evaluation test, referred to as “aged”) obtained in Example 2-6. It is a SEM image of the steam reforming catalyst composition (sample after gas evaluation test, referred to as “aged”) obtained in Example 2-7.
  • a steam reforming catalyst composition (hereinafter referred to as “the present catalyst composition") as an example of an embodiment of the present invention comprises catalytically active particles (hereinafter referred to as “the present catalyst particles”) containing a steam reforming catalyst active component and vanadium. And a steam reforming catalyst composition comprising
  • the form of the present catalyst composition may be any form such as powder, slurry, pellet, layered product and the like.
  • the present catalyst particles are catalytically active particles containing a steam reforming catalytically active component and vanadium. Vanadium reacts with the steam reforming catalyst active component to form a composite oxide. This complex oxide is gradually reduced by the reduction treatment for catalyst activation to express activity. The reduced active component is eventually deactivated by heat sintering, but due to hydrogen in the reforming reaction, the remaining complex oxide is newly reduced to exhibit activity. By repeating this cycle, the active ingredient can be supplied and as a result, the life of the catalyst can be extended.
  • vanadium in the catalyst particles containing the steam reforming catalytic active component such as nickel, reduction of the specific surface area after reduction activation is suppressed and the steam reforming performance is improved as compared to the case where vanadium is not contained. It is possible to further suppress the deterioration of the performance due to the sintering in the reduction activation treatment or the reforming reaction at a temperature of 500 ° C. or more.
  • the catalyst particles may be aggregated particles in which primary particles are aggregated, or particles in which the primary particles are monodispersed.
  • steam reforming catalyst active ingredient an element known to have an effect of promoting a steam reforming reaction can be used.
  • the steam reforming catalyst active component an element known to have an effect of promoting a steam reforming reaction.
  • at least one element of Fe, Ni, Co, Ru, Rh, Pt, Pd and Ir can be mentioned. Two or more of these may be used.
  • Ru or Rh is preferable in that it can further promote the steam reforming reaction and the conditions for reduction activation of the present catalyst composition can be relaxed.
  • the steam reforming catalytically active component may be present in the form of a metal (including an alloy), an oxide (including a complex oxide), or a mixture thereof, or a solid solution thereof, in particular in the form of an oxide or metal. Preferably it is present. That is, it is preferable to exist as an oxide in the state before the reduction activation treatment, and to exist in a state in which a part of the oxide is reduced, for example, a mixed state of metal and oxide after the reduction treatment.
  • vanadium In the catalyst particles, vanadium is preferably present in the form of an oxide, a metal, or a mixture thereof, or a solid solution thereof. That is, it exists as an oxide in the state before the reduction activation treatment, and after the reduction activation treatment, at least a part of vanadium is in a state in which the oxide is reduced, for example, a steam reforming catalyst active component such as Ni. It is preferable to form an alloy, to form a solid solution, or to exist in the form of a mixture of these.
  • the vanadium is preferably present on the surface of the catalytically active particles in order to efficiently act on the steam reforming catalytically active component. In particular, it is preferable to be present more on the surface than inside the catalytically active particles. Further, it is more preferable that the vanadium is present in a dispersed state on the surface of the catalytically active particles, without being unevenly distributed.
  • nickel hydroxide (Ni (OH) 2 ) is added in an aqueous solution containing a water-soluble vanadium compound, for example, vanadium such as ammonium vanadate (NH 4 VO 3 ).
  • the catalyst active particle powder such as particle powder may be put in, impregnated and fired. However, it is not limited to such a method.
  • the catalyst particles contain vanadium, sintering can be effectively suppressed.
  • vanadium in a proportion of 1 mol% or more with respect to 100 mol% of the steam reforming catalyst active component.
  • vanadium pentoxide is formed when producing the catalyst particles. Since there is a possibility of melting at the time of catalyst calcination, it is not preferable that the content of vanadium is too high.
  • the vanadium content is preferably contained in a proportion of 1 mol% or more with respect to 100 mol% of the steam reforming catalyst active component, more preferably 200 mol% or less, among them 2 mol% or more or 100 mol% or less Among them, it is particularly preferable to contain at a ratio of 3 mol% or more or 45 mol% or less.
  • the catalyst particles may have silicon oxide or zirconium oxide or both on the particle surface.
  • the catalyst particles are formed by the presence of a suitable amount of silicon oxide or zirconium oxide or both (also referred to as "surface oxide") on the surface of the present catalyst particles (also referred to as "core particles”) containing vanadium.
  • surface oxide silicon oxide or zirconium oxide or both
  • core particles silicon oxide or zirconium oxide or both
  • reduction activation treatment or reforming reaction is performed at a temperature of 500 ° C. or more without lowering the catalytic performance inherent to the present catalyst particles. It is possible to further suppress the sintering at the time. In particular, it is possible to further maintain the steam reforming catalyst performance after being exposed to a reducing environment or a high temperature environment of 550 ° C. or more for a long time.
  • examples of the silicon oxide include silicon suboxide (Si 3 O 2 ) and the like.
  • zirconium dioxide (ZrO 2 ) can be mentioned as the zirconium oxide.
  • At least one of Ca, Ba, Mg, Ti, Al, Ce, Hf, La, and V is provided on the surface of the present catalyst particles.
  • An element (referred to as "element A”) may be present. Two or more of these may be included. The presence of such an element A on the surface of the present catalyst particles can further enhance the steam reforming catalyst performance. Under the present circumstances, it is preferable that the said element A is disperse
  • silicon oxide, zirconium oxide and two or more of the elements A may be present in a mixed state, or silicon oxide, zirconium oxide, and the element A May exist separately.
  • the surface oxide may be present so as to cover the entire surface of the present catalyst particles, may be present in a layer having a certain thickness, or may be partially present on the surface of the core particles. There may be portions where the surface oxide is not present.
  • the surface coverage of silicon oxide or zirconium oxide (the ratio of 100% when silicon oxide or zirconium oxide is present on the entire surface of the catalyst particle) is 10% or more. It is preferable from the viewpoint of achieving sufficient steam reforming catalyst performance, and in particular, 20% or more or 100% or less from the viewpoint of the balance between steam reforming performance and heat resistance, among them 35% or more or 75% or less preferable.
  • the surface coverage of the silicon oxide or zirconium oxide and the surface coverage of the silicon compound or zirconium compound (when the silicon compound or zirconium compound is present on the entire surface of the catalyst particle is 100%,
  • the ratio of presence of the silicon compound or the zirconium compound is the same value. Therefore, in the examples described later, the surface coverage of the silicon compound or zirconium compound is calculated to be the surface coverage of the silicon oxide or zirconium oxide. Thus, even in the case of 100% coating, the gas flows through the micro cracks.
  • the ratio of the content of silicon oxide or zirconium oxide or both to 100 wt% of the core particles is preferably 2 to 15 wt% in the oxide state before reduction activation.
  • the ratio of the content of silicon oxide or zirconium oxide or both of them to 100 wt% of core particles is 2 wt% or more, the heat resistance effect can be exhibited, and if it is 15 wt% or less, A homogeneous product can be obtained.
  • 2 wt% or more or 5 wt% or less is particularly preferable.
  • the core particle powder is put in a solution containing silicon or zirconium or both and impregnated, and optionally dried and It can be formed by firing.
  • the silicon oxide or the zirconium compound can be oxidized to the silicon oxide or the zirconium oxide by surface-treating the core particle with a solution containing silicon or zirconium or both of them and then firing in the air. it can.
  • after surface-treating core particles using a silane coupling agent etc. they are dried if necessary, and then heat-treated at 300 ° C. or higher, preferably 400 to 600 ° C., to form the surface of the present catalyst particles.
  • the core particle powder is impregnated in a solution containing silicon or zirconium, for example, an ethanol solution of silicon alkoxide or zirconium alkoxide, dried as necessary, and then in a solution containing the element A as necessary.
  • the present catalyst particles may be impregnated with the catalyst particles, dried if necessary, and then fired to allow surface oxides to be present on the surfaces of the catalyst particles.
  • components other than the above may exist on the surface of the present catalyst particles.
  • an amount of 1 wt% or less based on Si or Zr present on the surface of the present catalyst particles does not affect the effect of the present catalyst composition, and allows any component to be contained. be able to.
  • the present catalyst composition may contain other components in addition to the present catalyst particles.
  • the oxide particle containing metal oxides such as an alumina, can be mentioned, for example. By containing such oxide particles, the present catalyst particles can be separated from each other, so that sintering can be prevented and the catalyst activity can be adjusted to a suitable level.
  • an oxide particle containing oxides such as Al, Ti, Si, Zr, and Ce, can be mentioned, for example.
  • a state in which the steam reforming catalyst active component is reduced by subjecting the present catalyst composition to a reduction treatment in is preferably from 0.1m 2 / g ⁇ 100m 2 / g, among others 0.5 m 2 / g or more or 75 m 2 / g or less, the at 5 m 2 / g or more or 65 m 2 / g or less among them Is particularly preferred.
  • a hydroxide of a steam reforming catalyst active component such as nickel hydroxide and an aqueous solution containing vanadium are mixed, and an appropriate time is obtained under appropriate conditions.
  • the mixture is allowed to stand so that the particles of the hydroxide are impregnated and adsorbed with the particles of the hydroxide, dried by evaporation to dryness, or filtered and dried, and then calcined at 300 to 600 ° C. (product temperature) in the air atmosphere (calcination)
  • the specific surface area of the steam reforming catalyst active component can be adjusted by adjusting the calcination temperature, the specific surface area of the nickel hydroxide and the like. However, it is not limited to such a method.
  • the catalyst composition can be prepared as follows. However, the manufacturing method described below is merely an example.
  • An aqueous solution containing vanadium (for example, an aqueous solution of ammonium vanadate) is mixed with a hydroxide powder or an oxide powder of at least one element selected from Fe, Ni, Co, Ru, Rh, Pt, Pd and Ir, Stir for 15 minutes to 12 hours at room temperature to 50 ° C. to impregnate and adsorb the vanadium on the hydroxide powder particles, heat to evaporate to dryness, or filter and dry, if necessary
  • the catalyst particles can be obtained by grinding accordingly.
  • the present catalyst particles thus obtained are impregnated as a core particle in a solution containing silicon or zirconium or both of them, if necessary
  • the material is calcined so as to maintain a temperature of 300 to 600 ° C. (material temperature) for 30 minutes to 6 hours in the air atmosphere, and then press-molded if necessary, and then 300 to 900 in the air atmosphere.
  • the catalyst composition can be obtained by calcining so as to maintain a temperature of 30 ° C. (material temperature) for 30 minutes to 6 hours, and pulverizing and sieving as required.
  • a steam reforming catalyst (hereinafter, referred to as "the present catalyst") as an example of an embodiment of the present invention is a catalyst formed using the present catalyst composition.
  • the present catalyst can be formed into an appropriate shape such as a pellet, and can be used alone as a catalyst, or can be used as a form supported on a substrate made of a ceramic or a metal material.
  • the material of the base examples include refractory materials such as ceramics and metal materials such as ferritic stainless steel.
  • the material of the ceramic base material is refractory ceramic material such as cordierite, cordierite-alpha alumina, silicon nitride, zircon mullite, alumina-silica magnesia, zircon silicate, sillimanite, magnesium silicate, zircon, Mention may be made of petalite, alpha alumina and aluminosilicates.
  • Examples of the material of the metal base include a refractory metal, such as stainless steel or a corrosion-resistant alloy containing iron as a main component.
  • the shape of the substrate may be honeycomb, pellet, or spherical.
  • the present catalyst is prepared by mixing and stirring the present catalyst composition, a binder and water to obtain a slurry, and applying the obtained slurry to a base material such as a ceramic honeycomb body, and calcining the obtained slurry on the base material surface.
  • a base material such as a ceramic honeycomb body
  • the catalyst layer may be a single layer or a multilayer of two or more layers.
  • Comparative Example 1 10 g of nickel hydroxide particle powder (specific surface area 120 m 2 / g) was calcined at 550 ° C. in the atmosphere for 3 hours to obtain a catalyst powder. To 8 g of the catalyst powder, 1.6 g of a 5 wt% PVA (polyvinyl alcohol) aqueous solution was added, dispersed uniformly in a mortar, placed in a 30 30 mm mold, and pressed into a disc at a pressure of 90 kN. The obtained disk-like molded product is calcined at 750 ° C.
  • PVA polyvinyl alcohol
  • Example 1 0.19 g of ammonium vanadate (NH 4 VO 3 ) was dissolved in 17.5 mL of pure water at 50 ° C. to prepare an aqueous ammonium vanadate solution. 10 g of nickel hydroxide particle powder (specific surface area 120 m 2 / g) was added to this aqueous solution of ammonium vanadate, and the mixture was stirred for 3 hours with a stirrer. Next, the resultant was heated to evaporate the water content, and the obtained solid was pulverized in a mortar and calcined at 550 ° C. in the atmosphere for 3 hours to obtain a catalyst powder.
  • NH 4 VO 3 ammonium vanadate
  • Example 2-1 In Example 1, the mixing ratio of ammonium vanadate (NH 4 VO 3 ) and nickel hydroxide particle powder (specific surface area 120 m 2 / g) was changed. That is, 0.39 g of ammonium vanadate (NH 4 VO 3 ) was dissolved in 36 mL of pure water at 50 ° C. to prepare an aqueous ammonium vanadate solution. 10 g of nickel hydroxide particle powder (specific surface area 120 m 2 / g) was added to the ammonium vanadate aqueous solution. A steam reforming catalyst composition (sample) comprising a V-added nickel-based catalyst active particle powder was prepared in the same manner as in Example 1 except for this point.
  • Example 2-2 In Example 1, the mixing ratio of ammonium vanadate (NH 4 VO 3 ) and nickel hydroxide particle powder (specific surface area 120 m 2 / g) was changed. That is, 0.66 g of ammonium vanadate (NH 4 VO 3 ) was dissolved in 65 mL of pure water at 50 ° C. to prepare an aqueous ammonium vanadate solution. 10 g of nickel hydroxide particle powder (specific surface area 120 m 2 / g) was added to the ammonium vanadate aqueous solution. A steam reforming catalyst composition (sample) comprising a V-added nickel-based catalyst active particle powder was prepared in the same manner as in Example 1 except for this point.
  • Example 2-3 In Example 1, the mixing ratio of ammonium vanadate (NH 4 VO 3 ) and nickel hydroxide particle powder (specific surface area 120 m 2 / g) was changed. That is, 1.25 g of ammonium vanadate (NH 4 VO 3 ) was dissolved in 115 mL of pure water at 50 ° C. to prepare an aqueous ammonium vanadate solution. 10 g of nickel hydroxide particle powder (specific surface area 120 m 2 / g) was added to the ammonium vanadate aqueous solution. A steam reforming catalyst composition (sample) comprising a V-added nickel-based catalyst active particle powder was prepared in the same manner as in Example 1 except for this point.
  • Example 2-4 In Example 1, the mixing ratio of ammonium vanadate (NH 4 VO 3 ) and nickel hydroxide particle powder (specific surface area 120 m 2 / g) was changed. That is, 2.23 g of ammonium vanadate (NH 4 VO 3 ) was dissolved in 205 mL of pure water at 50 ° C. to prepare an aqueous ammonium vanadate solution. 10 g of nickel hydroxide particle powder (specific surface area 120 m 2 / g) was added to the ammonium vanadate aqueous solution. A steam reforming catalyst composition (sample) comprising a V-added nickel-based catalyst active particle powder was prepared in the same manner as in Example 1 except for this point.
  • Example 2-5 In Example 1, the mixing ratio of ammonium vanadate (NH 4 VO 3 ) and nickel hydroxide particle powder (specific surface area 120 m 2 / g) was changed. That is, 5.4 g of ammonium vanadate (NH 4 VO 3 ) was dissolved in 500 mL of pure water at 50 ° C. to prepare an aqueous ammonium vanadate solution. 10 g of nickel hydroxide particle powder (specific surface area 120 m 2 / g) was added to the ammonium vanadate aqueous solution. A steam reforming catalyst composition (sample) comprising a V-added nickel-based catalyst active particle powder was prepared in the same manner as in Example 1 except for this point.
  • Example 2-6 In Example 1, the mixing ratio of ammonium vanadate (NH 4 VO 3 ) and nickel hydroxide particle powder (specific surface area 120 m 2 / g) was changed. That is, 8.5 g of ammonium vanadate (NH 4 VO 3 ) was dissolved in 770 mL of pure water at 50 ° C. to prepare an aqueous ammonium vanadate solution. 10 g of nickel hydroxide particle powder (specific surface area 120 m 2 / g) was added to the ammonium vanadate aqueous solution. A steam reforming catalyst composition (sample) comprising a V-added nickel-based catalyst active particle powder was prepared in the same manner as in Example 1 except for this point.
  • Example 2-7 In Example 1, the mixing ratio of ammonium vanadate (NH 4 VO 3 ) and nickel hydroxide particle powder (specific surface area 120 m 2 / g) was changed. That is, 12.6 g of ammonium vanadate (NH 4 VO 3 ) was dissolved in 1160 mL of pure water at 50 ° C. to prepare an aqueous ammonium vanadate solution. 10 g of nickel hydroxide particle powder (specific surface area 120 m 2 / g) was added to the ammonium vanadate aqueous solution. A steam reforming catalyst composition (sample) comprising a V-added nickel-based catalyst active particle powder was prepared in the same manner as in Example 1 except for this point.
  • Example 3 An aqueous solution of ammonium vanadate was prepared by dissolving 0.66 g of ammonium vanadate (NH 4 VO 3 ) in 65 mL of pure water at 50 ° C. 10 g of nickel hydroxide particle powder (specific surface area 120 m 2 / g) was added to this aqueous solution of ammonium vanadate, and the mixture was stirred for 3 hours with a stirrer. Next, the water was evaporated by heating, and the obtained solid was crushed in a mortar to obtain a powder sample.
  • NH 4 VO 3 ammonium vanadate
  • nickel hydroxide particle powder specific surface area 120 m 2 / g
  • a silane coupling agent (3-aminopropyltriethoxysilane, "KBE-903" manufactured by Shin-Etsu Silicone Co., Ltd., molecular weight 221.4) was added to 10 mL of water, and the precursor aqueous solution was uniformly stirred In addition, after stirring with a stirrer for 3 hours to uniformly coat the powder, the water was evaporated by heating to dry the sample. The obtained solid sample was pulverized in a mortar and calcined at 550 ° C. in the atmosphere for 3 hours to obtain a catalyst powder.
  • a silane coupling agent 3-aminopropyltriethoxysilane, "KBE-903" manufactured by Shin-Etsu Silicone Co., Ltd., molecular weight 221.4
  • Example 4 In the preparation of the aqueous precursor solution of Example 3, the procedure of Example 3 was repeated, except that 0.74 g of zirconium acetate (molecular weight: 327.4) was added to 10 mL of water instead of 0.78 g of the silane coupling agent.
  • a steam reforming catalyst composition (sample) was obtained comprising “V-added nickel-based catalytically active particle powder having zirconium oxide on the surface”.
  • Example 5 In preparation of the aqueous precursor solution of Example 3, instead of adding 0.78 g of a silane coupling agent (3-aminopropyltriethoxysilane, “KBE-903” manufactured by Shin-Etsu Silicone Co., Ltd.) to 10 mL of water, a silane coupling agent ( “Silicon oxide” in the same manner as in Example 3, except that 0.78 g of “KBE-903” manufactured by Shin-Etsu Silicone Co., Ltd., molecular weight 221.4 and 0.74 g of zirconium acetate (molecular weight 327.4) were added to 10 mL of water And a steam reforming catalyst composition (sample) comprising “V-added nickel-based catalyst active particle powder having zirconium oxide on the surface”.
  • a silane coupling agent 3-aminopropyltriethoxysilane, “KBE-903” manufactured by Shin-Etsu Silicone Co., Ltd.
  • Example 6 An aqueous solution of ammonium vanadate was prepared by dissolving 0.66 g of ammonium vanadate (NH 4 VO 3 ) in 65 mL of pure water at 50 ° C. After adding 10 g of nickel hydroxide particle powder (specific surface area 120 m 2 / g) to this ammonium vanadate aqueous solution and stirring with a stirrer for 3 hours, 0.1 mL of a ruthenium nitrate solution of Ru 50 g / L is added and stirring is further performed for 1 hour. The vanadium and ruthenium were sufficiently adsorbed on the surface of the nickel hydroxide particles.
  • the resultant was heated and evaporated to dryness to evaporate the water content, and the obtained solid was ground in a mortar to obtain a powder sample.
  • a silane coupling agent (3-aminopropyltriethoxysilane, "KBE-903" manufactured by Shin-Etsu Silicone Co., Ltd.) is added to 10 mL of water, and 0.74 g of zirconium acetate (molecular weight 327.4) is further added.
  • a uniformly stirred precursor aqueous solution was added, and stirred with a stirrer for 3 hours to uniformly coat the powder, and then the water was evaporated by heating and dried to obtain a solid sample sample.
  • the obtained solid sample was pulverized in a mortar and calcined at 550 ° C. in the atmosphere for 3 hours to obtain a catalyst powder.
  • 1.6 g of a 5 wt% PVA aqueous solution was added to 8 g of the catalyst powder, dispersed uniformly in a mortar, placed in a ⁇ 30 mm mold, and pressed into a disc at a pressure of 90 kN.
  • the obtained disk-like molded body is fired at 750 ° C.
  • a steam reforming catalyst composition (sample) was obtained, which was composed of “V ⁇ Ru-added nickel-based catalytically active particle powder in which silicon oxide and zirconium oxide are present on the surface” having a size of 0.5 mm to 4.0 mm.
  • Example 7 In Example 5, the mixing ratio of the aqueous precursor solution was adjusted to change the amount of silicon oxide present on the particle surface. That is, the silane coupling agent (3-aminopropyltriethoxysilane, "KBE-903" manufactured by Shin-Etsu Silicone Co., Ltd., “molecular weight 221.4”) was changed to 1.56 g, and further to zirconium acetate (molecular weight 327.4) 1.48 g . In the same manner as in Example 5 except this point, a steam reforming catalyst composition (sample) comprising "V-doped nickel-based catalyst active particle powder having silicon oxide and zirconium oxide present on the surface" was obtained.
  • the silane coupling agent 3-aminopropyltriethoxysilane, "KBE-903" manufactured by Shin-Etsu Silicone Co., Ltd., "molecular weight 221.4”
  • zirconium acetate molecular weight 327.4
  • this fuel reforming evaluation system is a city gas supplied from a cylinder as the gaseous fuel 1 (methane 89 to 90 vol%, ethane 4 to 6 vol%, propane 4 to 5 vol%, butane less than 1 vol%
  • pure water in the pure water tank 3 can be adjusted in flow rate by the gas mass flow controller 2 and the liquid mass flow controller 4, respectively.
  • the pure water passes through the vaporizer 6 in the electric furnace 5 to become water vapor, is mixed with the gaseous fuel in the fuel gas / steam mixing section 7, and is sent to the reforming catalyst 9 sealed in the stainless steel container in the electric furnace 8.
  • the gas reformed by the reforming catalyst 9 is exhausted through the bubbler 11. A part of the exhaust gas is sucked by a pump incorporated in a gas chromatograph (hereinafter referred to as “GC”) 13, and the reformed gas which has passed through the water removing unit 12 is quantified by the GC 13.
  • GC gas chromatograph
  • the S / C ratio was raised to 4.0 and the temperature was raised to 750 ° C. and maintained at 750 ° C. for 90 minutes.
  • the hydrogen content was returned to an A / C ratio of 2.5, lowered to 550 ° C., and then 10 minutes elapsed (Aged value).
  • the steam reforming catalyst composition (sample before gas evaluation test, referred to as "pre") obtained in the above examples and comparative examples, and after the above gas reforming evaluation test, that is, reduction activation treatment, measurement of hydrogen generation amount X-ray diffraction analyzer (Rigaku Co., Ltd.) for each of the steam reforming catalyst compositions (referred to as “Aged after”) collected by heating the samples that had undergone the accelerated deterioration test and the hydrogen generation amount to room temperature in a nitrogen atmosphere X-ray diffraction (XRD) measurement was carried out using RINT TTRIII)) (see FIGS. 3 to 6).
  • pre sample before gas evaluation test
  • Minimum covering area (m 2 / g) 6.02 x 10 23 x 13 x 10 -20 / surface treating agent molecular weight
  • Surface treating agent added amount (g) Ni (OH) 2 weight (g) x Ni (OH) 2 Specific surface area (m 2 / g) / minimum coverage area (m 2 / g)
  • the surface treatment agent indicates the silane coupling agent and zirconium acetate used in the above examples.
  • Table 2 the surface coverage of silicon oxide (silane coupling agent) or zirconium oxide (zirconium acetate) or a mixture of silicon oxide and zirconium oxide is shown as "coverage”.
  • Example 1 Each of the steam reforming catalyst compositions (samples) obtained in the above Example 1, Examples 2-1 to 2-2 and Examples 3 to 7 was used as an EDX of FE-SEM (manufactured by JSM-7001F / JEOL). It was confirmed that in any steam reforming catalyst composition, vanadium is present more on the surface than inside the catalytically active particles, and is not scattered on the surface of the catalytically active particles but on the surface. It could be confirmed that it exists in a dispersed state.
  • the thermal deterioration can be suppressed by the presence of the silicon oxide or the zirconium oxide or both of them on the surface of the catalytically active particles as described above, on the other hand, the silicon oxide or the zirconium oxide or these It was also found that the thermal characteristics can be improved and the thermal deterioration can be similarly suppressed by increasing the content of vanadium by a specific amount without both being present on the surface of the catalytically active particles.
  • the content of vanadium is increased by a specific amount without silicon oxide or zirconium oxide or both being present on the particle surface, a large amount of expensive vanadium must be contained, and the vanadium component is segregated And tend to be uneven. Therefore, in view of workability and cost, it can be considered preferable to have silicon oxide or zirconium oxide or both present on the surface of the catalytically active particles.

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Abstract

L'objectif de la présente invention est de fournir une nouvelle composition de catalyseur de reformage à la vapeur dans laquelle les performances de catalyseur ne diminuent pas même lors de réactions de reformage et de traitements de réduction à des températures de 500 °C ou plus. L'invention concerne une composition de catalyseur de reformage à la vapeur comprenant des particules catalytiquement actives qui contiennent : un composant catalytiquement actif de reformage à la vapeur qui a pour effet de favoriser la réaction de reformage à la vapeur; et du vanadium. L'addition de vanadium permet de réduire au minimum le frittage pendant une réaction de reformage ou un traitement de réduction à des températures de 500 °C ou plus et de réduire ainsi au minimum la détérioration des performances du catalyseur sans diminuer les performances d'origine du catalyseur du composant catalytiquement actif de reformage à la vapeur.
PCT/JP2015/076168 2014-09-24 2015-09-15 Composition de catalyseur de reformage à la vapeur et catalyseur de reformage à la vapeur WO2016047504A1 (fr)

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JP2020124704A (ja) * 2019-01-31 2020-08-20 大阪瓦斯株式会社 燃料改質触媒、燃料電池システム及び燃料電池セル構造体
CN112742412A (zh) * 2021-01-20 2021-05-04 成都理工大学 乙酸自热重整制氢用Mullite负载W促进Co基催化剂

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JP2020124704A (ja) * 2019-01-31 2020-08-20 大阪瓦斯株式会社 燃料改質触媒、燃料電池システム及び燃料電池セル構造体
JP7391683B2 (ja) 2019-01-31 2023-12-05 大阪瓦斯株式会社 燃料改質触媒、燃料電池システム及び燃料電池セル構造体
CN112742412A (zh) * 2021-01-20 2021-05-04 成都理工大学 乙酸自热重整制氢用Mullite负载W促进Co基催化剂
CN112742412B (zh) * 2021-01-20 2022-11-08 成都理工大学 乙酸自热重整制氢用Mullite负载W促进Co基催化剂

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