WO2019239936A1 - Corps de catalyseur poreux en oxyde de fer - Google Patents

Corps de catalyseur poreux en oxyde de fer Download PDF

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WO2019239936A1
WO2019239936A1 PCT/JP2019/021928 JP2019021928W WO2019239936A1 WO 2019239936 A1 WO2019239936 A1 WO 2019239936A1 JP 2019021928 W JP2019021928 W JP 2019021928W WO 2019239936 A1 WO2019239936 A1 WO 2019239936A1
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Prior art keywords
catalyst body
porous
iron oxide
noble metal
catalyst
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PCT/JP2019/021928
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English (en)
Japanese (ja)
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奈央 新見
洋平 直原
中山　鶴雄
悠輔 山内
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株式会社Ｎｂｃメッシュテック
国立研究開発法人物質・材料研究機構
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Priority to JP2020525451A priority Critical patent/JP7390663B2/ja
Publication of WO2019239936A1 publication Critical patent/WO2019239936A1/fr

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L9/00—Disinfection, sterilisation or deodorisation of air
    • A61L9/01—Deodorant compositions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/24—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by constructional aspects of converting apparatus
    • F01N3/28—Construction of catalytic reactors

Definitions

  • the present invention relates to a catalyst body capable of oxidatively decomposing organic components such as ethylene, carbon monoxide and ammonia in a gas.
  • exhaust gases generated from internal combustion engines such as automobiles and factories contain trace amounts of harmful components such as carbon monoxide, they are released into the atmosphere after they are removed using removal means.
  • a trace amount of malodorous substances may be produced and a mold odor may be generated, and various removal means are applied.
  • adsorption on an adsorbent such as activated carbon, radicals by a plasma generator, and decomposition and removal methods by active species such as ozone are widely used.
  • an adsorbent such as activated carbon, radicals by a plasma generator, and decomposition and removal methods by active species such as ozone are widely used.
  • active species such as ozone
  • a treatment method using active species such as plasma requires a generator of a certain size and is not a method that requires electric power to operate and can be used easily. Cannot be used due to concerns over the above changes.
  • a method of oxidative decomposition using a catalyst is widely used in addition to the method of oxidative decomposition using physically generated active species such as the plasma method described above.
  • the oxidation catalyst body in order to widen the contact area, a structure in which an active substance (catalyst particles) is supported on a carrier that is inorganic particles is used (Patent Document 1), or a membrane in which the active substance is made porous is used.
  • a method for treating a volatile organic compound is disclosed (Patent Document 4).
  • a catalyst body in which catalyst particles are supported in the pores of an inorganic mesoporous carrier having cylindrical mesopores, or a composition in which a catalyst is supported on a porous body of an inorganic layered compound (patent document) 5)
  • a catalyst body having a very wide specific surface area and high activity is obtained.
  • a catalyst using iron oxide is disclosed as a catalyst for promoting the oxidation reaction.
  • An amorphous iron oxide nanoparticle catalyst Patent Document 6
  • an iron oxide-based porous body having mesopores Patent Document 7
  • the catalyst body in which the oxidation catalyst particles are supported on the above-described cylindrical mesoporous support has a small pore diameter, so that it is difficult to permeate the gas to be treated at a high flow rate inside the pores. There is a problem that the catalyst efficiency of the catalyst body is lowered. Further, the catalyst bodies of Patent Documents 6 and 7 using iron oxide have a problem that the oxidation reaction requires a high temperature of 150 ° C. or higher. An object of this invention is to provide the catalyst body which can suppress the fall of catalyst activity when making flow volume large.
  • the gist of the present invention is as follows. [1] A thin piece containing iron oxide, at least a part of which is in a polycrystalline state, is formed by agglomerating in a state where there are a plurality of gaps communicating with the outside, and one gap communicates with another gap. A porous body having pores formed by, An oxidation catalyst particle comprising at least one selected from the group consisting of a noble metal, an oxide of the noble metal, and an alloy of the noble metal and a transition metal supported in the pores; The said thin piece is 5 nm or more and 20 nm or less in thickness, and the maximum length is 50 nm or more and 500 nm or less, The porous catalyst body characterized by the above-mentioned.
  • a catalyst member comprising: a base material that is an inorganic material; and the porous catalyst body according to any one of [1] to [4] that is held on a surface of the base material.
  • the treatment object comprising supplying the treatment gas to the porous catalyst body according to any one of [1] to [4] at a flow rate of 0.02 to 2.0 L / min / mg.
  • the present invention it is possible to provide a catalyst body that can suppress a decrease in catalytic activity when the flow rate is increased.
  • the catalyst body of the present embodiment has air permeability, and at least a part of the catalyst body is formed by agglomerating flakes containing iron oxide in a polycrystalline state in a state where there are a plurality of gaps communicating with the outside.
  • a porous body (support) having pores formed by one gap communicating with another gap, and oxidation of noble metal and noble metal supported in the pores of the porous body
  • oxidation catalyst particles containing at least one selected from the group consisting of alloys of noble metals and transition metals.
  • the flakes constituting the porous body have a thickness of 5 nm to 20 nm and a maximum length of 50 nm to 500 nm.
  • the catalyst body of the present embodiment is also simply referred to as a catalyst body.
  • the flakes are sometimes referred to as nanoflakes.
  • the porous body is formed by agglomerating nanoflakes or nanoflakes mass (a laminate of a plurality of nanoflakes). Specifically, the porous body is formed by agglomeration in a state where there is a gap communicating with the outside between the nanoflakes or nanoflakes, for example, the nanoflakes or nanoflakes are agglomerated in random directions. Is formed.
  • the communicating gap forms pores of the aggregate and provides the air permeability of the catalyst body. That is, in the porous body according to the present embodiment, there are pores formed by one opening portion of the surface of the aggregate being connected to another one or a plurality of opening portions.
  • the pores have a structure that provides the air permeability of the porous body.
  • the porous body is composed of thin pieces having the above-mentioned size, the porous body has a larger pore diameter and higher air permeability than a mesoporous porous body produced by decomposing and removing template molecules. It has a structure.
  • the oxidation catalyst particles (hereinafter simply referred to as oxidation catalyst particles) containing any of noble metals, noble metal oxides, and alloys of noble metals and transition metals on the surface of the nanoflakes in the pores of the porous body. Is also supported.
  • the gas to be treated diffuses into the catalyst body and comes into contact with the oxidation catalyst particles in the pores, and the organic gas contained in the gas to be treated It is oxidatively decomposed.
  • the pore size of the catalyst body of the present embodiment is larger than that of a mesoporous porous body and the air permeability is better, so that the gas to be treated can easily reach the oxidation catalyst particles inside the aggregate. Therefore, a decrease in catalyst activity when the flow rate is increased is suppressed, and the compound to be processed in the gas to be processed can be decomposed without reducing the processing speed as compared with the conventional method.
  • the shape of the catalyst body of the present embodiment can be various shapes such as powders, granules, and membranes, and is not particularly limited. In the case of a film, it is preferable that the catalyst body is held on the base material because handling becomes easy. At this time, whether or not the base material has air permeability is not particularly limited.
  • the membrane-like catalyst body of this embodiment is disposed on a non-breathable base material, irregularities may be formed on the surface of the catalyst body by embossing or the like. When irregularities are formed on the surface of the catalyst body, the contact area with the flowing gas increases, and the oxidation reaction of the compound to be treated can be further promoted.
  • the catalyst body of the present embodiment can decompose components such as organic gas, carbon monoxide, and ammonia in the gas to be treated into harmless substances such as carbon dioxide and water by an oxidation reaction, and can discharge them to the atmosphere.
  • Specific compounds that can be treated in the catalyst body of the present embodiment are not particularly limited, but carbon monoxide contained in exhaust gas from an internal combustion engine, tobacco smoke, and the like, nitrogen-containing compounds such as ammonia, agricultural products, Compounds emitted from plants such as flower buds, substances that volatilize from materials such as automobile interior materials, housing building materials / interior materials, housings / members of home appliances, substances that volatilize from organic solvents such as paints, adhesives, and cleaning agents Etc.
  • hydrocarbons such as methane, ethane, propane, butane, ethylene, propylene, isoprene, benzene, xylene, toluene, ethylbenzene, styrene, ⁇ -farnesene, ⁇ -farnesene, methanol, ethanol, propane-1- All, butan-1-ol, pentan-1-ol, hexane-1-ol, heptane-1-ol, octan-1-ol, trans-2-hexenol, cis-2-hexenol, trans-3-hexenol, Alcohols such as cis-3-hexenol, linalool, benzyl alcohol, formaldehyde, acetaldehyde, propionaldehyde, butanal, pentanal, nonanal, benzaldehyde, hexanal, trans-2-hexenal, c
  • the diameter of the pore diameter is not particularly limited, but may be 2 nm or more, for example.
  • the shape of the pores and the positional relationship between the openings are not particularly limited.
  • the average pore diameter is desirably 10 nm or more and 100 nm or less.
  • the pore diameter is 10 nm or more, a catalyst body with higher air permeability is obtained, the gas to be treated is likely to permeate and diffuse, and a decrease in catalyst activity when the flow rate is increased is further suppressed.
  • the pore diameter exceeds 100 nm, it is necessary to increase individual nanoflakes. However, since the production requires a lot of cost, 100 nm or less is preferable.
  • the diameter of the pores of the porous body according to the present embodiment can be calculated by a mercury intrusion method, for example, using an automatic specific surface area / pore distribution measuring device by the mercury intrusion method. . Whether or not the flakes are aggregates and whether or not the gaps formed by the flakes are communicating (in other words, whether the porous body has pores) are determined by three-dimensional scanning electrons. It can be confirmed with a microscope (SEM).
  • the porous body having pores according to the present embodiment is configured to include iron oxide, and at least a part of the iron oxide is in a polycrystalline state (hereinafter sometimes referred to as polycrystalline iron oxide). Any of them can be used and are not particularly limited.
  • the iron oxide it can be exemplified FeO, the Fe 2 O 3, Fe 3 O 4 iron oxide that is stable.
  • the iron oxide in a polycrystalline state refers to an iron oxide formed by collecting a large number of microcrystals in a random direction, and the microcrystal means a single crystal having a crystallite diameter of 10 nm or less. To do.
  • a part of the polycrystalline iron oxide according to the present embodiment may have an amorphous region. Whether or not it contains polycrystalline iron oxide can be determined by observation with X-ray diffraction (XRD) and high-resolution transmission electron microscope (TEM).
  • the condition can be the condition shown in the embodiment, for example.
  • the thickness of the thin piece containing the polycrystalline iron oxide has an average value of 5 nm or more and 20 nm or less, and the maximum length is an average value of 50 nm or more and 500 nm or less.
  • the maximum length means the maximum length on the surface of the flake (the surface having the largest area).
  • thickness means the length orthogonal to the surface (surface which has the largest area). The thickness and the maximum length can be obtained as an average value obtained by calculating the flake size in an image photograph of a transmission electron microscope (TEM).
  • the catalyst body can be used in the form of being held on various forms of substrates such as honeycombs and meshes.
  • the catalyst body When the catalyst body is held on the base material, if the iron oxide of the support is crystalline, the adhesive strength to the base material is not high, and it may be peeled off from the base material during production or use.
  • the iron oxide when the iron oxide is amorphous, it can be more easily and strongly bonded to a base material, particularly a metal base material, by a sintering process. Further, for the same reason, when the catalyst particles are fired, the catalyst particles can be bonded more strongly to the iron oxide of the porous body, and the decrease in the catalyst activity due to the movement of the catalyst particles and the enlargement of the catalyst particles can be suppressed. .
  • the flakes constituting the support according to the present embodiment may contain other components in order to improve various properties such as durability.
  • Components other than iron oxide that can be contained are not particularly limited, but in consideration of the fact that heating may be performed in the step of supporting the catalyst particles on the support, it may be a heat-resistant material that does not deteriorate at a heating temperature or higher. preferable.
  • substances contained in the flakes other than iron oxide include, for example, Al 2 O 3 , TiO 2 , ZrO 2 , SnO 2 , SiO 2 , MgO, ZnO 2 , Bi 2 O 3 , In 2 O 3 , MnO 2 , Mn 2 O 3 , Nb 2 O 5 , Sb 2 O 3 , CuO, Cu 2 O, NiO, Ni 3 O 4 , Ni 2 O 3 , CoO, Co 3 O 4 , Co 2 O 3 , WO 3 , CeO 2 And single inorganic oxides such as Pr 6 O 11 , Y 2 O 3 , In 2 O 3 , PbO, and ThO 2 .
  • cerium-zirconium-bismuth composite oxide is a solid solution represented by the general formula Ce 1-X-Y Zr X Bi Y O 2- ⁇ , X, Y, the value is 0.1 ⁇ X ⁇ each [delta] 0 .3, 0.1 ⁇ Y ⁇ 0.3, 0.05 ⁇ ⁇ ⁇ 0.15.
  • the material of the flakes can be selected according to the type of gas to be treated, the equipment to which the catalyst body is applied, and various environmental conditions, and may contain iron oxide in a polycrystalline state, and is not particularly limited.
  • the oxidation catalyst particles are supported on the surface of the flakes in the gap.
  • the oxidation catalyst particle is not particularly limited as long as it includes at least one of a noble metal having a catalytic function for promoting an oxidation reaction, a noble metal oxide, and an alloy of a noble metal and a transition metal.
  • noble metals refer to gold, silver and platinum group ruthenium, rhodium, palladium, osmium, iridium and platinum.
  • the noble metal oxide is an oxide of the above-mentioned noble metal or a hydrate thereof, specifically, Au 2 O 3 , Ag 2 O, AgO, Ag 2 O ⁇ Ag 2 O 3 , RuO 2 , RuO 4 , Rh 2 O 3 , PdO, OsO 2 , OsO 4 , IrO 2 , Ir 2 O 3 .nH 2 O, PtO 2 , PtO 2 .H 2 O, platinum black and the like can be mentioned.
  • the transition metal of the alloy is not particularly limited as long as it can form an alloy with a noble metal, but Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, W, Os, Ir, etc. are mentioned.
  • oxidation catalyst particles may be configured to include Preferred constituents of oxidation catalyst particles include Au, Pt, Pd, Au 2 O 3 , Ag 2 O, AgO, Ag 2 O ⁇ Ag 2 O 3 , PdO, PtO 2 , PtO 2 ⁇ H 2 O, platinum black, etc. For example, one or more of these may be included in the oxidation catalyst particles.
  • the average particle diameter of the oxidation catalyst particles is not particularly limited, but if it is 9 nm or less (more preferably 1 nm or more and 9 nm or less, and even more preferably 2 nm or more and 6 nm or less), the specific surface area of the oxidation catalyst particles increases and the catalytic activity is increased. Is significantly improved and the decomposition efficiency of the compound to be treated in the gas to be treated is further increased, which is preferable.
  • the average particle diameter of the oxidation catalyst particles can be obtained as an average value obtained by calculating the particle size in an image photograph of a transmission electron microscope (TEM).
  • the oxidation catalyst particles are preferably supported at 0.1 to 20% by mass, and preferably 0.5 to 10% by mass with respect to the catalyst body of the present embodiment (a porous body containing the oxidation catalyst particles). More preferred. When it is supported in an amount of more than 20% by mass, the oxidation catalyst particles tend to aggregate and the catalytic activity is reduced as compared with the case where the oxidation catalyst particles are within the range. Moreover, if it is less than 0.1 mass%, compared with the case where it exists in a range, since sufficient catalyst activity cannot be obtained, it is unpreferable.
  • the catalyst body of the present embodiment may include promoter particles and various metal elements, and is not particularly limited.
  • the catalyst may be a mixture of cocatalyst particles and oxidation catalyst particles obtained by combining the cocatalyst and the oxidation catalyst particles, or a composite catalyst composed of composite particles obtained by combining various metal elements with the oxidation catalyst particles.
  • the oxidation catalyst particles may be within the above-mentioned size range.
  • the size of the composite particles may be within the above-mentioned size range.
  • Examples of the metal particles (nanoparticles) other than the catalyst particles used in the promoter or composite catalyst include base metals and oxides thereof. Two or more kinds of these noble metals and oxides thereof, base metals and oxides thereof may be mixed and supported in the pores of the porous body.
  • the catalyst body of this embodiment can be obtained by producing a porous body formed by agglomerating flakes containing iron oxide, and then supporting the oxidation catalyst particles on the pores of the porous body.
  • the porous body can be obtained by dissolving or dispersing an iron compound such as iron salt or iron alkoxide in a solvent, heat-treating it to produce a solid content, and firing the solid content.
  • solvents examples include protic solvents such as water, alcohols, and carboxylic acids, and ketones, and one or a mixture of these can be used. Even if the solvent is a solid at room temperature, it can be used as long as it is a fluid such as a liquid, a gas, or a supercritical fluid at the time of heat treatment.
  • Examples of the alcohols include methanol, ethanol, propanol, butanol, pentanol, hexanol, methoxymethanol, ethoxymethanol, methoxyethanol, ethoxyethanol, benzyl alcohol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, triethylene glycol, tetra Mention may be made of ethylene glycol, pentaethylene glycol, dipropylene glycol, tripropylene glycol, glycerol, mannitol, sorbitol and the like.
  • carboxylic acids examples include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, oleic acid, linoleic acid, linolenic acid, arachidonic acid, lactic acid, malic acid, citric acid, benzoic acid, And pyruvic acid.
  • ketones examples include acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, cyclohexanone, isophorone, and acetophenone.
  • alcohols because the pore diameter of the porous body becomes larger, and it is more preferable to use a mixture of two or more alcohols.
  • iron salts include inorganic salts such as iron hydroxide salts, halogen salts, sulfates, nitrates, and carbonates, and organic salts such as oxalates and lactates.
  • any of a divalent iron salt and a trivalent iron salt can be used, and it may be a double salt of the above iron salt or may have crystal water.
  • the iron alkoxide include iron (III) triethoxide, iron (III) tripropoxide, iron (III) triisopropoxide and the like.
  • a metal element other than iron or an inorganic or organic salt of silicon may be dissolved or dispersed in a solvent together with an iron compound.
  • Metal elements other than iron include Al, Ti, Zr, Sn, Si, Mg, Zn, Bi, In, Mn, Nb, Sb, Cu, Ni, Co, W, Ce, Pr, Y, Pb, Th, etc. Is mentioned.
  • the iron compound it is desirable to add the iron compound to the solvent in the range of 0.001 mol to 0.1 mol with respect to 1 L of the solvent.
  • the amount is less than 0.001 mol with respect to 1 L of the solvent, the product concentration is lower than in the case where the amount is within the range, and therefore, the loss during the manufacturing operation increases.
  • the amount is more than 0.1 mol, the iron compound may not completely react as compared with the case of being in the range, which is not preferable.
  • An iron oxide precursor that is a solid content is obtained by performing a heat treatment on a solution in which an iron compound is dissolved or dispersed, for example, in a pressure vessel.
  • heating temperature is not specifically limited, For example, it is preferable to set it as 100 to 400 degreeC.
  • the heating temperature is less than 100 ° C., the conversion from the iron compound to the iron oxide precursor may not sufficiently proceed as compared with the range.
  • the heating temperature is higher than 400 ° C., the porous structure tends to collapse compared to the range.
  • the heat treatment time can be appropriately set by those skilled in the art depending on the heating temperature, and is not particularly limited, but it is preferably performed in the range of 3 hours to 24 hours.
  • the firing temperature of the solid content is preferably 200 ° C. or higher and 1000 ° C. or lower, and more preferably 200 ° C. or higher and 500 ° C. or lower.
  • the firing time is not particularly limited and can be appropriately set by those skilled in the art, but it is preferably performed for 2 hours or more.
  • the calcination temperature is lower than 200 ° C. or the calcination time is shorter than 2 hours, the conversion from the iron oxide precursor to iron oxide may be insufficient as compared with the case where it is within the range.
  • the firing temperature is higher than 500 ° C., the nanoflakes constituting the porous body collapse in shape as compared with the case where the firing temperature is within the range, and the specific surface area of the porous body decreases. Moreover, when it exceeds 1000 degreeC, shape collapse will further advance easily.
  • the oxidation catalyst particles are supported on the pores of the support to obtain the catalyst body of this embodiment.
  • a support or a colloidal solution (hereinafter referred to as a noble metal compound solution) in which a noble metal compound and / or a noble metal compound corresponding to a noble metal oxide contained in an oxidation catalyst particle to be supported is brought into contact with the support is contacted.
  • a noble metal compound solution is introduced into the pores.
  • a solution obtained by further dissolving a transition metal salt in addition to the compound corresponding to the noble metal may be used as the noble metal compound solution.
  • the noble metal compound solution is immersed in a sodium borohydride solution or a hydrogen reduction method in which a baking treatment at 200 to 600 ° C. and a exposure to a hydrogen stream at 100 to 300 ° C. are performed.
  • the oxidation catalyst particles can also be obtained in the pores by performing a known reduction operation such as a liquid phase reduction method.
  • the oxidation catalyst particles can be obtained in the pores only by heating and baking at 200 to 600 ° C. without performing the above-described known reduction operation.
  • the reduction of the noble metal compound is limited to a part, and for example, the noble metal alone and the noble metal oxide may coexist in the oxidation catalyst particles in the pores.
  • Examples of the metal compound corresponding to the noble metal or noble metal oxide constituting the oxidation catalyst particle include, as gold compounds, HAuCl 4 ⁇ 4H 2 O, NH 4 AuCl 4 , KauCl 4 ⁇ nH 2 O, KAu (CN) 4 , Na 2 AuCl 4 , KauBr 4 ⁇ 2H 2 O, NaAuBr 4 etc., platinum compounds are chloroplatinic acid, dinitrodiammine platinum, dichlorotetraammine platinum, etc., and palladium compounds are dinitrodiammine palladium, ammonium chloropalladate, etc. Can be mentioned.
  • the concentration of the noble metal compound in the noble metal compound solution is not particularly limited, but it is preferable to prepare the solution at 1 ⁇ 10 ⁇ 2 to 1 ⁇ 10 ⁇ 5 mol / L because the generated oxidation catalyst particles are unlikely to aggregate.
  • the transition metal salt in the noble metal compound solution is not particularly limited as long as it is a compound that can be dissolved and does not cause precipitation even when coexisting with a metal compound corresponding to the above-mentioned noble metal or noble metal oxide. And halides such as bromide, nitrates, carbonates, bicarbonates, carboxylates and the like.
  • the concentration of the transition metal salt in the noble metal compound solution is not particularly limited, but it is preferable to prepare the solution as 1 ⁇ 10 ⁇ 2 to 1 ⁇ 10 ⁇ 5 mol / L because the generated oxidation catalyst particles are unlikely to aggregate.
  • the catalyst body of the present embodiment can be held on the substrate as described above. It is preferable to hold the catalyst body of the present embodiment on the base material because the film thickness of the catalyst body of the present embodiment can be easily reduced when forming the film.
  • the base material may be a non-breathable structure such as a plate shape or a breathable structure.
  • the air-permeable structure include a sheet-like structure in which a large number of through-holes are formed by punching, a fiber, a cloth, a mesh, and a fiber made of a woven fabric, a net, a nonwoven fabric, or the like.
  • a structure (filter shape) can be mentioned.
  • various shapes and sizes suitable for the purpose of use can be used as appropriate.
  • the catalyst body may be formed on the surface of the base material to be held on the base material. Since the base material on which the catalyst body is formed may be heated when the support of the catalyst body is formed, it is desirable to use a heat-resistant material that can withstand the heating temperature. Specifically, metal materials, ceramics, glass, carbon fibers, silicon carbide fibers, heat resistant organic polymer materials, and the like are preferable, and metals, metal oxides, and glass are more preferable.
  • examples of ceramics used for the base material include ceramics such as earthenware, ceramics, stoneware and porcelain, and ceramics such as glass, cement, gypsum, enamel and fine ceramics.
  • the composition of the ceramics to be composed can include elemental, oxide-based, hydroxide-based, carbide-based, carbonate-based, nitride-based, halide-based, phosphate-based, etc. It may be a composite.
  • ceramics used for the base material barium titanate, lead zirconate titanate, ferrite, alumina, forsterite, zirconia, zircon, mullite, steatite, cordierite, aluminum nitride, silicon nitride, carbonized Examples thereof include silicon, new carbon, and new glass, and ceramics such as high-strength ceramics, functional ceramics, superconducting ceramics, nonlinear optical ceramics, antibacterial ceramics, biodegradable ceramics, and bioceramics.
  • titania, zirconia, alumina, ceria (cerium oxide), zeolite, apatite, silica, activated carbon, diatomaceous earth, and the like can be used as the base material.
  • metal oxides such as chromium, manganese, iron, cobalt, nickel, copper, and tin can be used for the substrate.
  • polyimide polyether ether ketone, polyphenylene sulfide, polyaramid, polybenzothiazole, polybenzoxazole, polybenzimidazole, polyquinoline, polyquinoxaline, fluororesin, etc.
  • thermosetting such as phenol resin and epoxy resin
  • a heat-resistant organic polymer material known to those skilled in the art, such as an adhesive resin.
  • Such members and devices include filters such as air purifiers, air conditioners, refrigerators, air purification filters installed in warehouses and showcases, packaging materials for fruits and flowers, exhaust gas purification devices such as internal combustion engines, etc. And a steam reformer of a fuel cell.
  • filters such as air purifiers, air conditioners, refrigerators, air purification filters installed in warehouses and showcases, packaging materials for fruits and flowers, exhaust gas purification devices such as internal combustion engines, etc.
  • a steam reformer of a fuel cell a fuel cell.
  • the catalyst body of this embodiment You may make it provide.
  • FIG. 1 An SEM photograph of the obtained iron oxide porous body is shown in FIG.
  • the specific surface area, pore volume, and pore diameter of the iron oxide porous body were 145 m 2 / g, 0.41 g / cm 3 , and 13.9 nm, respectively.
  • Example 2 A gold-supported iron oxide catalyst body was obtained in the same manner as in Example 1 except that the iron oxide porous body in Production Example 1 was changed to the iron oxide porous body in Production Example 2.
  • the average particle diameter of gold in the obtained gold-supported iron oxide catalyst was observed with a TEM, it was 3.2 nm.
  • the amount of gold supported on the catalyst body was 12.9% by mass as measured by an atomic absorption photometer.
  • Example 3 A gold-supported iron oxide catalyst body was obtained in the same manner as in Example 1 except that the iron oxide porous body in Production Example 1 was changed to the iron oxide porous body in Production Example 3.
  • the average particle diameter of gold in the obtained gold-supported iron oxide catalyst was observed with a TEM, it was 3.6 nm.
  • the amount of gold supported on the catalyst body was 9.8% by mass as measured with an atomic absorption photometer.
  • Comparative Example 1 A commercially available gold-supported iron oxide catalyst (RR2Fe manufactured by Halta Gold Co., Ltd.) was used for the catalyst body of Comparative Example 1. As a result of measurement by the BET method, the specific surface area of the catalyst body was 83 m 2 / g, and no pores were observed. When the average particle diameter of gold was observed by TEM, it was 1.8 nm. The amount of gold supported on the catalyst body was 0.8% by mass as measured by an atomic absorption photometer.
  • RR2Fe manufactured by Halta Gold Co., Ltd.
  • Example 2 A gold-supported iron oxide catalyst body was obtained in the same manner as in Example 1 except that the iron oxide porous body in Production Example 1 was replaced with the iron oxide porous body in Production Example 4. When the average particle diameter of gold was observed with TEM, it was 2.6 nm. The amount of gold supported on the catalyst body was 11.0% by mass as measured with an atomic absorption photometer.
  • CO removal test Using carbon monoxide (CO), the CO oxidation reaction of the catalyst bodies of Examples and Comparative Examples was evaluated. Specifically, a test apparatus is prepared in which a glass substrate on which the catalyst bodies of Examples and Comparative Examples are fixed is installed in a channel so as to have a predetermined channel width and height (width 5 cm, height 1 mm). did. A gas to be treated was prepared by mixing carbon monoxide (concentration 1,000 ppm) and air, and the gas to be treated was supplied to the flow path while controlling the flow rate with a mass flow controller, and a CO removal test was performed. The results are shown in Table 1.
  • an infrared spectrophotometer (FTIR-6000, manufactured by JASCO Corporation) equipped with a gas cell having a long optical path (2.5 m) was used.
  • the reaction conditions were a carbon monoxide concentration of 1,000 ppm, an oxygen concentration of 20%, a relative humidity of 50%, a reaction temperature of 25 ° C., and a treatment time of 1 hour.
  • a catalyst amount of 4 mg was used, and in Comparative Example 1, a catalyst amount of 40 mg was used.
  • the gas flow rates were 0.1, 1.0, and 5.0 L / min (Examples 1-3 and Comparative Example 2).
  • the CO removal rates of Examples 1 to 3 were 94% or more at a gas flow rate of 0.1 L / min, which was higher than 27.7% of Comparative Example 1. Further, at a gas flow rate of 1.0 L / min, both were 60% or more, which was a higher removal rate than Comparative Examples 1 and 2. It can be said that the catalyst body of the example works with a higher CO removal rate even when the gas flow rate is increased.

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Abstract

La présente invention concerne un corps de catalyseur poreux caractérisé en ce qu'il contient : un corps poreux, dans lequel des flocons contenant de l'oxyde de fer, dont au moins certains sont dans un état polycristallin, sont formés en étant agrégés dans un état selon lequel une pluralité de vides qui se connectent à l'extérieur sont présents et les flocons ont des pores fins formés par un vide lié à un autre vide ; ainsi que des particules de catalyseur d'oxyde supportées dans les pores fins et contenant au moins un type choisi dans le groupe constitué par un métal noble, un oxyde du métal noble, un alliage du métal noble et un métal de transition, les flocons ayant une épaisseur de 5 à 20 nm et une longueur maximale de 50 à 500 nm. La présente invention est capable de fournir un corps de catalyseur qui peut supprimer une diminution de l'activité catalytique à un débit accru.
PCT/JP2019/021928 2018-06-11 2019-06-03 Corps de catalyseur poreux en oxyde de fer WO2019239936A1 (fr)

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