WO2022158473A1 - Catalyseur, procédé et dispositif de reformage de carburant - Google Patents

Catalyseur, procédé et dispositif de reformage de carburant Download PDF

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Publication number
WO2022158473A1
WO2022158473A1 PCT/JP2022/001721 JP2022001721W WO2022158473A1 WO 2022158473 A1 WO2022158473 A1 WO 2022158473A1 JP 2022001721 W JP2022001721 W JP 2022001721W WO 2022158473 A1 WO2022158473 A1 WO 2022158473A1
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fuel
catalyst
fuel reforming
reforming catalyst
component
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PCT/JP2022/001721
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English (en)
Japanese (ja)
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紘一郎 本田
裕基 中山
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エヌ・イーケムキャット株式会社
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Priority to JP2022576708A priority Critical patent/JPWO2022158473A1/ja
Publication of WO2022158473A1 publication Critical patent/WO2022158473A1/fr

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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
    • B01J23/58—Platinum group metals with alkali- or alkaline earth 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
    • 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
    • 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

Definitions

  • the present invention relates to a fuel reforming catalyst, and more particularly, a fuel reforming catalyst, a fuel reforming method, and a fuel reforming method for reforming a fuel containing hydrocarbons with steam to reform a synthesis gas containing hydrogen. Concerning quality equipment.
  • an exhaust gas recirculation (EGR) system takes in part of the exhaust gas after combustion and reintakes it in order to reduce nitrogen oxides and improve fuel efficiency.
  • EGR exhaust gas recirculation
  • a fuel reforming engine system in which a heat exchange type fuel reformer and a fuel supply means (fuel injection valve) are combined with an EGR system, and a part of the fuel is passed through the fuel reformer and then burned in the cylinder. is proposed.
  • a fuel reforming engine system has the advantage of greatly improved thermal efficiency compared to a conventional EGR system. This utilizes H 2 O (water vapor) contained in the exhaust gas from the internal combustion engine and the heat of the exhaust gas to generate hydrogen and carbon monoxide from a portion of the fuel through a steam reforming reaction. It improves thermal efficiency by supplying it together with fuel to the internal combustion engine.
  • the heat of the exhaust gas is used for the endothermic reaction of the steam reforming reaction.
  • active species used in the steam reforming reaction include rhodium (Rh), platinum (Pt), palladium (Pd), ), ruthenium (Ru), iridium (Ir), and other highly active platinum group metals are used as reforming catalysts.
  • Patent Document 1 discloses the formula: A′ 1-x A′′ x B′ 1-y B′′ y O 3 (wherein A′ is lanthanum (La) and/or cerium (Ce), A " is at least one of lanthanum, calcium (Ca), samarium (Sm), cerium, strontium (Sr), barium (Ba), and praseodymium (Pr), and B' is cobalt (Co), iron (Fe), At least one of manganese (Mn) and gadolinium (Gd), and B′′ is ruthenium (Ru) and rhodium (Rh).) is used as a fuel reforming catalyst. is proposed.
  • A′ is lanthanum (La) and/or cerium (Ce)
  • a " is at least one of lanthanum, calcium (Ca), samarium (Sm), cerium, strontium (Sr), barium (Ba), and praseodymium (Pr)
  • B' is cobal
  • Patent Document 2 proposes a steam reforming catalyst in which Ru and Ir and/or Rh are carried on a carrier whose main component is alumina.
  • Patent Document 3 discloses that at least one active ingredient A selected from Pt, Pd, Ir, Rh and Ru, molybdenum (Mo), vanadium (V), tungsten (W), chromium (Cr) and rhenium (Re) , Co, Ce, and Fe, an oxide thereof, an alloy thereof, or a mixture thereof.
  • active ingredient A selected from Pt, Pd, Ir, Rh and Ru, molybdenum (Mo), vanadium (V), tungsten (W), chromium (Cr) and rhenium (Re) , Co, Ce, and Fe, an oxide thereof, an alloy thereof, or a mixture thereof.
  • Patent Document 4 a composite oxide support containing alumina (Al 2 O 3 ), ceria (CeO 2 ), zirconia (ZrO 2 ), and a rare earth oxide other than ceria supports a platinum group metal.
  • a steam reforming catalyst is proposed in which the surface composition of aluminum in the composite oxide support is 1.5 times or more the aluminum composition of the entire support.
  • Patent Document 5 proposes a steam reforming catalyst in which rhodium, which is an active metal species, is supported on a ceria-zirconia-alumina composite oxide support, and discloses that steam reforming of E20 gasoline was performed.
  • Patent Document 1 JP-A-2001-224963
  • Patent Document 2 JP-A-2008-55252
  • Patent Document 3 JP-A-2008-149313
  • Patent Document 4 JP-A-2016-165712
  • Patent Document 5 JP-A-2008-149313 2018-143988 publication
  • the present invention has been made in view of the above problems, and it is an object of the present invention to provide a fuel reforming catalyst that has excellent reforming activity and excellent durability against deterioration factors such as catalyst poisoning. Another object of the present invention is to provide a fuel reforming method and a fuel reforming engine system using a fuel reforming catalyst.
  • the present inventors have found that instead of using a conventionally used platinum group compound such as rhodium alone as a metal active species of a reforming fuel catalyst, platinum group
  • platinum group The present inventors have noticed that the coexistence of a compound and a co-catalyst component such as a rare earth compound as a metal active species significantly improves the reforming activity as compared with a conventional single platinum group catalyst.
  • a co-catalyst component such as a rare earth compound as a metal active species significantly improves the reforming activity as compared with a conventional single platinum group catalyst.
  • the gist of the present invention is as follows.
  • a fuel reforming catalyst for reforming a fuel containing hydrocarbons into a synthesis gas containing hydrogen, a catalyst component and a co-catalyst component containing a platinum group metal element; a carrier that supports the catalyst component and the co-catalyst component; with A fuel reforming catalyst, wherein the promoter component comprises at least one element selected from the group consisting of scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, barium, nickel, and strontium.
  • the promoter component contains at least one element selected from the group consisting of scandium, yttrium, lanthanum, praseodymium, neodymium, promethium, samarium, europium, barium, nickel, and strontium;
  • the fuel reforming catalyst described [3] The fuel reforming catalyst according to [1] or [2], wherein the promoter component is supported in an amount of 50 parts by mass or more and 1000 parts by mass or less with respect to 100 parts by mass of the catalyst component. .
  • a fuel reforming engine system comprising reforming and adding the resulting hydrogen and carbon monoxide to a fuel supplied to an internal combustion engine.
  • the present invention it is possible to realize a fuel reforming catalyst that has high reforming activity at low temperatures (about 400°C to 600°C) and has excellent durability against deterioration factors such as catalyst poisoning.
  • fuel can be efficiently reformed even at low temperatures (about 400° C. to 600° C.), and fuel containing sulfur components can also be efficiently reformed. becomes possible.
  • a fuel reforming catalyst is a fuel reforming catalyst for reforming a fuel containing hydrocarbons into a synthesis gas containing hydrogen, and comprises a catalyst component containing a platinum group metal element and an assistant. It comprises a catalyst component and a carrier supporting the catalyst component and the co-catalyst component.
  • the catalyst component and the co-catalyst component supported on the carrier may be collectively referred to as "catalyst active species”.
  • a member holding a fuel reforming catalyst that is, a catalyst comprising a catalyst component, a co-catalyst component, and a carrier supporting both components is sometimes called a "base material".
  • the catalyst component used in the fuel reforming catalyst according to the invention comprises a platinum group metal element.
  • platinum group metal elements include ruthenium (Ru), rhodium (Rh), palladium (Pd), osmium (Os), iridium (Ir), and platinum (Pt). From the viewpoint of activity, Ru, Rh, Pd and Pt are preferred, and Rh and Pt are more preferred. These elements may be used alone or in combination of two or more.
  • Examples of combining two or more platinum group elements are not particularly limited, but a combination of two or more platinum group elements with excellent oxidation activity, a combination of two or more platinum group elements with excellent reduction activity, and platinum with excellent oxidation activity.
  • a combination of a group element and a platinum group element having excellent reduction activity can be mentioned.
  • a combination of a platinum group element having excellent oxidation activity and a platinum group element having excellent reduction activity is preferable as one aspect of the synergistic effect.
  • the combination of Pd and Rh, the combination of Pt and Rh, and the combination of Ru and Rh are preferred, and among these, the combination of Pt and Rh is more preferred.
  • the ratio is not particularly limited, but the platinum group metal element other than Rh is usually 1 part by mass or more, preferably 5 parts by mass, per 100 parts by mass of Rh. Above, it is more preferably 10 parts by mass or more, while the upper limit is usually 500 parts by mass or less, preferably 300 parts by mass or less, more preferably 200 parts by mass or less.
  • the ratio is within the above range, the performance as a fuel reforming catalyst is improved, and deactivation by poisoning substances such as sulfur can be suppressed.
  • the fuel reforming catalyst according to the present invention is characterized by containing, as catalytically active species, a promoter component selected from specific elements in addition to the catalyst component selected from the platinum group metal elements described above.
  • a promoter component selected from specific elements in addition to the catalyst component selected from the platinum group metal elements described above.
  • conventional platinum in addition to the platinum group metal element that has been conventionally used as a catalytically active species of a fuel reforming catalyst, by coexisting a specific element described later as a metal active species (promoter component), conventional platinum Remarkably improved reforming activity compared to a single platinum group catalyst, and surprisingly, it maintains stable reforming activity for a long period of time even in the presence of sulfur, which is a catalyst poison for platinum group catalysts. be able to. Although the reason for this is not clear, it is considered as follows.
  • the co-catalyst component exerts an electronic interaction with the catalyst component, and the catalyst component (platinum group element) is likely to act.
  • the catalyst component platinum group element
  • Rh is likely to be reduced by the co-catalyst component, and the catalytic activity is considered to be improved compared to the case where Rh alone is used as the catalyst component.
  • the co-catalyst component has a carrier structure
  • the presence of the co-catalyst component and the co-catalyst component on the surface of the carrier allows the co-catalyst component acts as acid and base sites on the carrier, and acts as a buffer for carbon deposition, which tends to progress at acid sites, and sulfur poisoning, which tends to progress at basic sites, and improves the durability of the catalyst component.
  • the above-mentioned specific element as a co-catalyst component exhibits the properties of both acids and bases in addition to favorable electronic interaction with the catalyst component.
  • co-catalyst components examples include scandium (Sc), yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), and neodymium (Nd).
  • Nd is particularly preferable, from the viewpoint of hydrogen generating ability and deactivation resistance due to sulfur content.
  • cerium is preferable for catalytic activity, long-term durability is a problem depending on the type of fuel (especially when even a small amount of sulfur is contained).
  • the ratio of the catalyst component and the co-catalyst component is not particularly limited, but the co-catalyst component is usually 10 parts by mass or more, preferably 50 parts by mass or more, more preferably 100 parts by mass or more with respect to 100 parts by mass of the catalyst component. , the upper limit is usually 2000 parts by mass or less, preferably 1000 parts by mass or less.
  • the ratio of both is within the above range, the catalytic activity (fuel reforming ability) of the catalyst component selected from platinum group metal elements is improved, and deactivation by poisoning substances such as sulfur can be suppressed.
  • the blending ratio means the total sum.
  • the amount of the above-described catalytically active species supported is not particularly limited, and may be appropriately supported according to the desired design conditions, cost requirements, etc., but it is 0.05 mass per 100 parts by mass of the support in terms of metal. It is preferably from 0.1 part to 20 parts by mass, and more preferably from 0.1 part by mass to 15 parts by mass. If the supported amount of the catalytically active species is small, there is a tendency that sufficient catalytic activity cannot be obtained in the steam reforming reaction of the fuel composed of hydrocarbons. There is a tendency that the catalytic activity per unit amount of active species does not improve. Considering both catalyst performance and cost, the amount of supported catalytically active species is more preferably 0.4 parts by mass or more and 8 parts by mass or less with respect to 100 parts by mass of the carrier.
  • the catalytically active species (catalyst component and co-catalyst component) supported on the carrier are preferably supported in the form of particles.
  • the particle diameter of the catalytically active species is preferably 1 to 100 nm, more preferably 2 to 50 nm, from the viewpoint of catalytic activity. If the particle size of the catalytically active species is too small, it tends to become an oxide state that does not exhibit catalytic activity. Activity tends to decrease.
  • the catalytically active species have a predetermined particle size as described above, for example, a catalyst component supply source (for example, platinum group metal nitrate or acetate) and a promoter component supply source (for example , Nitrate or acetate of the above-described predetermined element), impregnating the support with a predetermined amount of the solution, and then calcining the support to support the catalyst on the support.
  • the particle diameter of the catalyst particles can be adjusted by controlling the concentration of the solution (concentration of catalytically active species), the impregnation amount of the solution, and the calcination conditions (temperature and time).
  • the fuel reforming catalyst according to the present invention has the above-described catalytically active species supported on a carrier, but may contain other components other than the catalytically active species.
  • the ratio of the catalytically active species is preferably 70% by mass or more, more preferably 90% by mass or more, and particularly 95% by mass or more (100% by mass including).
  • the carrier for supporting the catalytically active species described above is not particularly limited, and known carriers can be used, but inorganic oxides can be preferably used from the viewpoint of durability.
  • examples include alumina (Al 2 O 3 ) such as ⁇ , ⁇ , ⁇ , ⁇ , zirconia (ZrO 2 ), titania (TiO 2 ), silica (SiO 2 ), and ceria (CeO 2 ). These may be used singly or in combination of two or more, or may be composite oxides thereof.
  • alumina is preferably used from the viewpoint of durability.
  • the carrier used in the fuel reforming catalyst of the present invention is preferably a porous body.
  • the porous body may have a BET specific surface area of 30 m 2 /g to 600 m 2 /g.
  • a carrier is produced by a conventionally known method as described later.
  • a slurry is prepared by kneading a catalytically active species component, a carrier component, a binder, a pore-forming agent, a solvent, etc., using a ball mill or the like, and after molding into a desired shape, drying and firing are carried out to obtain a pore-forming agent and a slurry.
  • the binder is removed and pores are formed in the carrier.
  • the average pore diameter is preferably 0.5 nm or more and 100 nm or less, more preferably 1 nm or more and 50 nm or less, from the viewpoint of diffusion of the fuel gas and contact with the catalyst. More preferably, the thickness is 2 nm or more and 10 nm or less. This is because if the pore diameter in the carrier is too large, the number of times of contact with the catalyst is reduced and the reaction is difficult to proceed, and if the pore diameter is too small, the fuel gas is difficult to diffuse and the reaction is similarly difficult to proceed.
  • the average pore size is determined by measuring the pore size of 10 arbitrarily selected individual carriers using a nitrogen adsorption type pore distribution meter or the like, and calculating the average value of these 10 pore sizes. can be obtained by
  • the fuel reforming catalyst of the present invention can be used alone, it may be held on a suitable substrate.
  • the base material is not particularly limited, and known ones can be used.
  • the above inorganic or metallic materials may be used singly or in combination of two or more.
  • alumina, silica, mullite, cordierite, stainless steel, and silicon carbide are preferred, and cordierite, stainless steel, and silicon carbide are more preferred.
  • preferably 80% by mass or more, more preferably 90% by mass or more, and particularly preferably 99% by mass or more (including 100% by mass) of the entire substrate is made of the above material. .
  • the base material may contain other components with the above-described material as a main component.
  • Fe 2 O 3 , SiO 2 , Na 2 O, etc. which are known to improve the heat resistance of the carrier, may be added to the above materials.
  • the shape of the substrate is not particularly limited, and various shapes such as spherical, cylindrical, bead, pellet, prismatic, tablet, needle, film, honeycomb monolith, etc. can be used depending on the application. can do. Among these, beads, pellets, and honeycomb monoliths are preferred. Therefore, it is particularly preferable that the substrate according to a preferred embodiment of the present invention is made of alumina, silica, mullite, cordierite, or stainless steel, and has a bead, pellet, or honeycomb monolith shape. I can say
  • the average diameter of the substrate is preferably 0.5 mm or more and 10 mm or less, and 0.7 mm or more, from the viewpoint of handleability and fluidity in a container. It is more preferably 5 mm or less, and even more preferably 1 mm or more and 3 mm or less.
  • the average diameter (diameter) of the carrier is preferably 1 mm or more and 10 mm or less, and more preferably 1 mm or more and 5 mm or less, from the viewpoint of handling properties and fluidity in the container. is more preferred.
  • the average diameter of the carrier is obtained by observing with an optical microscope or the like, measuring the major and minor diameters of 100 arbitrarily selected carriers (catalyst particles), and calculating the average of the major and minor diameters as the particle diameter. , can be obtained by calculating the average particle size of 100 individual particles.
  • the fuel reforming catalyst described above can be obtained by supporting a catalytically active species component (catalyst component and cocatalyst component) on a carrier.
  • the supporting method is not particularly limited, and conventionally known methods can be applied.
  • a carrier is impregnated with a mixed catalyst solution containing the nitrate or acetate of the above-described predetermined element, and then reduction or calcination is performed to precipitate catalytically active species components on the carrier in the form of particles. can be done.
  • the catalyst component supply source is first impregnated into the carrier, and then the support is impregnated with the promoter component supply source, and then the two are supported by reduction or calcination.
  • the promoter component supply source is first impregnated. may be impregnated into the carrier, and then the catalyst component supply source may be impregnated into the carrier and then reduced or calcined to support both.
  • a fuel reforming catalyst can be produced by performing treatments such as washing, calcination, and hydrogen reduction.
  • the above platinum group metal element (catalyst component) or rare earth element or alkaline earth element (promoter component) acetate, carbonate, nitrate, ammonium salt, citrate, dinitro Diammine salts and the like or their complexes can be mentioned.
  • the platinum group metal element is rhodium, rhodium (Rh) acetates, carbonates, nitrates, ammonium salts, citrates, dinitrodiamine salts, etc. or their of which nitrates are preferred.
  • platinum group metal element is platinum
  • the fuel reforming catalyst of the present invention when used in a fuel reforming device for internal combustion engines, for example, it is preferable to use the fuel reforming catalyst in a state in which it is held in a substrate such as a honeycomb monolith.
  • a method for manufacturing a fuel reforming honeycomb catalyst for an internal combustion engine using the fuel reforming catalyst of the present invention will be described below.
  • a metal salt of a catalyst component, a metal salt of a co-catalyst component, a carrier, and optionally a binder, a dispersant and a solvent are mixed to prepare a slurry solution, and the slurry solution is applied to a honeycomb monolith by a wash coating method or the like.
  • a honeycomb catalyst holding the fuel reforming catalyst can be obtained by impregnating the substrate with the slurry solution and firing the substrate impregnated with the slurry solution.
  • the solvent for the slurry solution is not particularly limited, but examples include solvents such as water (preferably pure water such as ion-exchanged water and distilled water). Although the concentration of such a metal salt solution is not particularly limited, it is preferably 0.001 mol/L or more and 0.5 mol/L or less as ions of the metal salt.
  • the temperature at which the base material impregnated with the slurry solution is fired is not particularly limited, but is usually 200°C or higher and 800°C or lower. If the calcination temperature is too low, the supply source of the catalytically active species element will not be sufficiently thermally decomposed, making it difficult to enter a metal state exhibiting catalytic activity, which tends to lower the activity. On the other hand, if the calcination temperature is too high, the supported catalytically active species element tends to become coarse particles and the catalytic activity in the steam reforming reaction of the fuel composed of hydrocarbons tends to decrease.
  • the firing time can also be adjusted as appropriate, but it is usually preferably 0.1 hours or more and 100 hours or less. If the calcination time is too short, the source material of the catalytically active species element will not be sufficiently thermally decomposed, and it will be difficult to change to a metallic state that exhibits catalytic activity, so the activity tends to decrease. On the other hand, even if the firing time is longer than necessary, no effect can be obtained, and the cost and the production amount per unit time tend to decrease.
  • the amount of supported catalytically active species can be measured with an ICP emission spectrometer.
  • the promoter component can be supported in an amount of 50 parts by mass or more and 1000 parts by mass or less with respect to 100 parts by mass of the catalyst component.
  • the fuel reforming catalyst according to the present invention can be used not only for EGR applications in internal combustion engines, but also as a single catalyst as it is, and can be used as a catalyst in various devices involved in steam reforming reactions.
  • it can be applied to a hydrogen plant such as an oil refinery, a hydrogen production device for a fuel cell in a stationary distributed power source, a hydrogen production device from natural gas, and the like.
  • Hydrocarbons can be steam reformed by using the fuel reforming catalyst according to the present invention. That is, a hydrocarbon containing fuel can be contacted with a fuel reforming catalyst in the presence of water vapor to produce hydrogen and carbon monoxide.
  • the fuel containing hydrocarbons and steam may be independently supplied to the reactor, or they may be mixed in advance and then supplied to the reactor.
  • steam it is preferable to use a method of providing the reactor with the exhaust gas after combustion with hydrogen after reforming.
  • the hydrocarbons contained in the fuel are not particularly limited, and examples thereof include alkanes, alkenes, alkynes, aromatic compounds, alcohols, aldehydes, etc.
  • methane Linear or branched saturated aliphatic hydrocarbons such as ethane, propane, butane, pentane, hexane, heptane, octane, nonane, and decane; alicyclic saturated hydrocarbons such as cyclohexane, methylcyclohexane, and cyclooctane;
  • gaseous or liquid hydrocarbons having 2 to 12 carbon atoms such as polycyclic aromatic hydrocarbons are preferable, and hydrocarbons having 2 to 8 carbon atoms are more preferable.
  • saturated aliphatic hydrocarbons are preferred, and 50% or more of the fuel is more preferably saturated aliphatic hydrocarbons.
  • biomass fuel composed of hydrocarbons such as ethanol, gasoline, diesel fuel (light oil), natural gas, hydrocarbon gas, and biodiesel can be used.
  • a mixed fuel of ethanol and gasoline can be used.
  • ethanol has a high octane number
  • gasoline with a low octane number (for example, in the range of 30 to 85)
  • ethanol an octane number in the range of 80 to 100, which is equivalent to that of ordinary gasoline fuel, can be obtained.
  • the fuel reforming method of the present invention is used from the viewpoint that it is liquid at normal temperature, is easy to handle, has high safety, has high affinity with water (steam), and is easy to obtain.
  • natural gas methanol, ethanol and gasoline, and more preferably ethanol, gasoline and mixed fuels of ethanol and gasoline.
  • the mixing ratio of the fuel containing hydrocarbons and the water vapor contained in the exhaust gas is not particularly limited.
  • the molar ratio of water vapor to carbon (S/C) is preferably 0.2 to 10, more preferably 0.4 to 2.
  • the temperature of the reforming reaction is preferably 250-800°C, more preferably 350-700°C.
  • a fuel containing hydrocarbons can be reformed even at a low temperature of 400° C. or less, which has conventionally been difficult to steam reform a fuel containing hydrocarbons due to low catalytic activity. becomes possible.
  • by supplying the exhaust gas after combustion of the internal combustion engine to the reactor as a heat source it becomes unnecessary to prepare a separate heat source, which is advantageous in terms of structure and cost.
  • the fuel reforming catalyst according to the present invention is excellent in resistance to sulfur poisoning, it can exhibit stable catalytic performance over a long period of time even when the fuel contains a sulfur component.
  • Sulfur components contained in the fuel include, for example, S, S 2 ⁇ , SO, SO 2 , SO 3 , SO 4 2 ⁇ and compounds containing S.
  • Main sources of sulfur components include contact with sulfur components contained in fuel and sulfur components contained in exhaust gas after fuel combustion.
  • the EGR system which uses gasoline as a fuel and exhaust gas from an internal combustion engine as a steam and heat source, has a simple reformer structure and is advantageous in terms of cost, but the amount of contact between the fuel reforming catalyst and the sulfur content also increases. , the problem of reduced catalyst life tends to occur.
  • the fuel reforming method using the fuel reforming catalyst according to the present invention can improve the thermal efficiency by combining it with the EGR system. For example, by using the steam contained in the post-combustion exhaust gas from an internal combustion engine, the fuel containing hydrocarbons is brought into contact with the fuel reforming catalyst according to the present invention in the presence of steam, thereby partially or entirely converting the fuel. By reforming into hydrogen and carbon monoxide and adding the obtained hydrogen and carbon monoxide to the fuel supplied to the internal combustion engine, the thermal efficiency of the engine can be improved.
  • Example 1 ⁇ -alumina powder (average particle size: 28 ⁇ m, BET specific surface area: 141 m 2 /g) was impregnated with an aqueous solution of neodymium nitrate and dried. Next, ⁇ -alumina powder impregnated with an aqueous solution of neodymium nitrate (approximately 25 wt% in terms of Nd 2 O 3 ) was impregnated with an aqueous solution of rhodium nitrate (approximately 7 wt% in terms of Rh). After baking for 30 minutes, a rhodium-neodymium-supported alumina precursor was obtained.
  • the amount of hydrogen generated is relative to the amount of hydrogen generated by the same operation using a reaction tube filled with powder obtained in the same manner as in Example 1 except that only rhodium was used as a catalytically active species. value.
  • the measured hydrogen generation amount was as shown in Table 1 below.
  • Example 1 A catalyst-supporting alumina powder was prepared in the same manner as in Example 1, except that the ⁇ -alumina powder was not impregnated with the aqueous solution of neodymium nitrate, and the reaction tube was filled with the powder to measure the amount of hydrogen generated. The evaluation results were as shown in Table 1 below.
  • Examples 2 to 9 Catalyst-supported alumina powder was prepared in the same manner as in Example 1 except that the neodymium nitrate aqueous solution was changed to the metal nitrate aqueous solution shown in Table 1 and the supported amount was as shown in Table 1, and the reaction tube was filled with hydrogen generation amount. was measured.
  • the catalyst components, co-catalyst support amount, and hydrogen generation amount of each catalyst were as shown in Table 1 below.
  • ⁇ -alumina powder (average particle size: 28 ⁇ m, BET specific surface area: 141 m 2 /g) was impregnated with an aqueous solution of neodymium nitrate (approximately 25 wt % in terms of Nd 2 O 3 ) and dried.
  • neodymium nitrate approximately 25 wt % in terms of Nd 2 O 3
  • the ⁇ -alumina powder impregnated with the neodymium nitrate aqueous solution was impregnated with a platinum salt solution (manufactured by NECC, product name: A-solt) and dried.
  • the ⁇ -alumina powder impregnated with the platinum salt aqueous solution was impregnated with the rhodium nitrate aqueous solution described above and dried in the same manner as in Example 1 to prepare a catalyst-supporting alumina powder, which was filled in a reaction tube to generate hydrogen. Quantitative measurements were made.
  • the catalyst components, co-catalyst support amount, and hydrogen generation amount of each catalyst were as shown in Table 1 below.
  • Example 13 In Example 1, by changing the impregnation amount of the solution to the carrier, a catalyst-supporting alumina powder with a catalyst-supporting amount of 1.33% by mass of rhodium and 4.0% by mass of neodymium was prepared, and the obtained rhodium- Nitric acid and water were added to the neodymium-supported alumina powder to adjust the pH to 4 to 5, followed by wet pulverization with a ball mill to an average particle size of 12 ⁇ m to prepare a slurry solution of the catalyst-supported alumina powder.
  • honeycomb base material made of cordierite (number of cells/mil thickness: 600 cpsi/3.5 mil) was prepared, and the end of the honeycomb base material was immersed in the slurry solution, and from the opposite end side of the honeycomb base material, Vacuum suction was applied to impregnate the substrate surface with the slurry solution (wash coat amount: 150 g/L).
  • the honeycomb base material impregnated with the slurry solution in this manner was dried at 150° C. and fired at 450° C. in an air atmosphere to obtain a catalyst-carrying honeycomb base material.
  • the amount of catalyst supported on the catalyst-supported honeycomb substrate was 2.0 g/L for Rh and 6.0 g/L for neodymium.
  • Example 2 A catalyst-supporting honeycomb substrate was produced in the same manner as in Example 13 except that a catalyst-supporting alumina powder slurry with a catalyst-supporting amount of 2% by mass of rhodium was used, and the washcoat amount was 100 g/L. We evaluated the amount of hydrogen generated over time. The amounts of hydrogen generated in Example 13 and Comparative Example 2 at 0 seconds were almost the same.
  • Example 13 Even when the supported catalyst (Example 13) is used for reforming a fuel containing sulfur, compared with a conventional supported catalyst (equivalent to Comparative Example 2) consisting only of a platinum group metal element, It can be seen that the decrease in the amount of hydrogen generated is gradual, and the durability against deterioration factors such as catalyst poisoning is excellent.

Abstract

L'invention fournit un catalyseur de reformage de carburant excellent en termes d'activité de reformage et de durabilité vis-à-vis de facteurs de dégradation tels que l'empoisonnement du catalyseur. Plus précisément, l'invention concerne un catalyseur de reformage de carburant destiné à reformer un carburant contenant un hydrocarbure en gaz de synthèse contenant un hydrogène. Ce catalyseur de reformage de carburant comporte : un composant catalyseur ainsi qu'un composant promoteur catalytique contenant des éléments métalliques du groupe platine ; et un support supportant lesdits composant catalyseur et composant promoteur catalytique. Ledit composant promoteur catalytique contient au moins une sorte d'élément choisie dans un groupe constitué d'un scandium, d'un yttrium, d'un lanthane, d'un cérium, d'un praséodyme, d'un néodyme, d'un prométhium, d'un samarium, d'un europium, d'un baryum, d'un nickel et d'un strontium.
PCT/JP2022/001721 2021-01-20 2022-01-19 Catalyseur, procédé et dispositif de reformage de carburant WO2022158473A1 (fr)

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JPH022879A (ja) * 1988-03-12 1990-01-08 Satoru Igarashi 炭化水素の水蒸気改質用触媒
JP2011088066A (ja) * 2009-10-22 2011-05-06 Jx Nippon Oil & Energy Corp 改質用触媒、改質装置および水素製造装置
WO2013136821A1 (fr) * 2012-03-14 2013-09-19 エヌ・イーケムキャット株式会社 Composition de catalyseur pour l'épuration des gaz d'échappement et catalyseur pour l'épuration des gaz d'échappement d'automobile
JP2014113518A (ja) * 2012-12-06 2014-06-26 Nissan Motor Co Ltd 燃料改質触媒
JP2015196142A (ja) * 2014-04-02 2015-11-09 株式会社豊田中央研究所 水蒸気改質触媒、それを用いた水蒸気改質方法、及び水蒸気改質反応装置
JP2016104467A (ja) * 2014-12-01 2016-06-09 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 炭化水素含有ガスの水蒸気改質触媒、水素製造装置、及び水素製造方法
JP2019203487A (ja) * 2018-05-25 2019-11-28 株式会社豊田中央研究所 燃料改質装置及びその制御方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH022879A (ja) * 1988-03-12 1990-01-08 Satoru Igarashi 炭化水素の水蒸気改質用触媒
JP2011088066A (ja) * 2009-10-22 2011-05-06 Jx Nippon Oil & Energy Corp 改質用触媒、改質装置および水素製造装置
WO2013136821A1 (fr) * 2012-03-14 2013-09-19 エヌ・イーケムキャット株式会社 Composition de catalyseur pour l'épuration des gaz d'échappement et catalyseur pour l'épuration des gaz d'échappement d'automobile
JP2014113518A (ja) * 2012-12-06 2014-06-26 Nissan Motor Co Ltd 燃料改質触媒
JP2015196142A (ja) * 2014-04-02 2015-11-09 株式会社豊田中央研究所 水蒸気改質触媒、それを用いた水蒸気改質方法、及び水蒸気改質反応装置
JP2016104467A (ja) * 2014-12-01 2016-06-09 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 炭化水素含有ガスの水蒸気改質触媒、水素製造装置、及び水素製造方法
JP2019203487A (ja) * 2018-05-25 2019-11-28 株式会社豊田中央研究所 燃料改質装置及びその制御方法

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