WO2009084208A1 - 多孔質成形体及びその製造方法、並びに触媒用担体及び触媒 - Google Patents

多孔質成形体及びその製造方法、並びに触媒用担体及び触媒 Download PDF

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Publication number
WO2009084208A1
WO2009084208A1 PCT/JP2008/003971 JP2008003971W WO2009084208A1 WO 2009084208 A1 WO2009084208 A1 WO 2009084208A1 JP 2008003971 W JP2008003971 W JP 2008003971W WO 2009084208 A1 WO2009084208 A1 WO 2009084208A1
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WIPO (PCT)
Prior art keywords
magnesium
molded body
aluminum
catalyst
porous molded
Prior art date
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PCT/JP2008/003971
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English (en)
French (fr)
Inventor
Shinji Takahashi
Naoya Kobayashi
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Toda Kogyo Corporation
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Filing date
Publication date
Application filed by Toda Kogyo Corporation filed Critical Toda Kogyo Corporation
Priority to US12/810,232 priority Critical patent/US9388082B2/en
Priority to EP08868580.5A priority patent/EP2226308B1/en
Priority to KR1020107013878A priority patent/KR101458661B1/ko
Publication of WO2009084208A1 publication Critical patent/WO2009084208A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/08—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by adding porous substances
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/10—Magnesium; Oxides or hydroxides thereof
    • 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
    • B01J23/005—Spinels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • 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
    • B01J23/78—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 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/393—Metal or metal oxide crystallite size
    • 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
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/613—10-100 m2/g
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
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    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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    • B01J8/06—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
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    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
    • C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
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    • 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
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    • C01B3/583—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids including a catalytic reaction the reaction being the selective oxidation of carbon monoxide
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    • C01B3/586—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids including a catalytic reaction the reaction being a methanation reaction
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
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    • C04B35/443—Magnesium aluminate spinel
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
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    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
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    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
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    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
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    • 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 porous molded body comprising at least magnesium and aluminum and a method for producing the same, and more specifically, a porous molded body having both a specific surface area and mechanical properties, wherein a filter, a desiccant, A porous material composed of magnesium and aluminum having a large amount of fine pores, high specific surface area, and high strength, which can be suitably used for adsorbents, purification agents, deodorants, catalyst carriers, etc.
  • An object of the present invention is to provide a molded product and a method for producing the same.
  • An object of the present invention is to provide a porous molded body made of magnesium and aluminum which can be produced industrially in large quantities and has excellent sulfur poisoning resistance.
  • ceramic porous bodies have excellent heat resistance, impact resistance, chemical resistance, normal temperature and high temperature strength characteristics, light weight, etc., so various filters (gas separation, solid separation, sterilization, dust removal, etc.), drying It is widely used as an agent, adsorbent, purification agent, deodorant, catalyst carrier, sound absorbing material, heat insulating material, sensor, etc., and has become an indispensable industrial material.
  • the ceramic porous body When used for these applications, there are various demands on the pore distribution and pore volume of the ceramic porous body. For example, when used as a catalyst support, a high pore volume is required so that a large amount of the supported component can be supported. Furthermore, when used in a fixed bed facility as a catalyst carrier or adsorbent, it is necessary to have a high strength that does not easily cause crushing during extraction or filling of the catalyst, and has a high pore volume and a high strength that have both of these functions. A ceramic molded body is required.
  • the alumina porous body used as various filters and catalyst carriers is mainly ⁇ -alumina, but ⁇ -alumina undergoes a phase transition to ⁇ -alumina, which is a stable phase at around 1000 ° C, and the specific surface area is significantly reduced. There was a problem that the function as a catalyst carrier was lost.
  • Patent Documents 1 to 4 There are reports of general alumina-based compacts and magnesia compacts.
  • Patent Document 1 describes an ⁇ -alumina molded body, which is a molded body with high mechanical strength, but has a small BET specific surface area.
  • Patent Documents 2 and 3 describe an alumina molded body, which has a large pore volume and a large BET specific surface area but a low mechanical strength.
  • magnesia is formed into a high-strength molded body by compression molding, but there is no description of the BET specific surface area, pore volume, etc., but it is easily estimated that it is small.
  • a ceramic porous body As a ceramic porous body generally used, there is an ⁇ -alumina molded body, but the specific surface area value is small because the crushing strength is increased by sintering by high-temperature firing.
  • the inorganic binder is accompanied by a decrease in performance due to the pores of the porous powder particles being added, and if added in a large amount to increase the mechanical strength, the weight increases.
  • the performance degradation of the porous structure becomes large.
  • sintering requires high-temperature treatment from the viewpoint of strength, the pores and specific surface area are damaged due to the alteration of the crystal structure of the porous powder particles, and the burden of heat energy cost is inevitably increased.
  • the present invention relates to a porous molded body made of at least magnesium and aluminum and a method for producing the same, and more specifically, a porous molded body having both a specific surface area and mechanical properties, and a filter, From magnesium and aluminum having a high specific surface area and high strength, including a large amount of fine pores, which can be suitably used as an agent, adsorbent, purification agent, deodorant, catalyst carrier, etc.
  • An object of the present invention is to provide a porous molded body and a method for producing the same.
  • Another object of the present invention is to provide a porous molded body made of magnesium and aluminum, which is excellent in sulfur poisoning resistance and can be industrially produced in large quantities.
  • the present invention is a porous molded body comprising at least magnesium and aluminum, containing 10 to 50 wt% magnesium as magnesium atoms, 5 to 35 wt% aluminum as aluminum atoms, and having a pore volume of 0.01 to A porous molded body having a mean pore diameter of 0.5 cm 3 / g, an average pore diameter of 300 mm or less, and an average crushing strength of 3 kg or more (Invention 1).
  • the present invention is the porous molded body having a BET specific surface area of 10 to 100 m 2 / g (Invention 2).
  • the present invention is the porous molded body formed by molding hydrotalcite containing magnesium and aluminum and firing it in the range of 500 ° C. to 1500 ° C. (Invention 3).
  • the present invention is a catalyst carrier using the porous molded body according to any one of the present inventions 1 to 3 (Invention 4).
  • the present invention is a catalyst using the porous molded body according to any one of the present inventions 1 to 3 (Invention 5).
  • the porous molded body according to the present invention is composed of at least magnesium and aluminum, and has excellent mechanical strength while having a large BET specific surface area and pore volume.
  • the porous molded body according to the present invention is a porous molded body having both a specific surface area and mechanical properties, and is suitable for a filter, a desiccant, an adsorbent, a purification agent, a deodorant, a catalyst carrier, and the like. .
  • the porous molded body obtained by the present invention exhibits a high specific surface area and strength even when kept at a high temperature, a steam reforming catalyst used at a high temperature, a catalyst for producing dimethyl ether by dehydrating methanol, a CO shift catalyst, In a catalyst such as a CO selective oxidation catalyst and a methanation catalyst, it is useful as a catalyst carrier for supporting a catalyst component.
  • the porous molded body according to the present invention contains a large amount of magnesium, it is suitable as a catalyst carrier for reforming hydrocarbons such as city gas and LPG containing a large amount of sulfur components.
  • porous molded body according to the present invention will be described.
  • the porous molded body according to the present invention is a compound composed of at least magnesium and aluminum.
  • elements such as sodium, calcium, silicon, iron, nickel, zinc, may be contained.
  • other components those derived from raw materials remaining after the heat treatment described in the following production method, for example, oxygen, hydroxyl group, oxalic acid group, sulfate group, sulfite group, nitrate group, chlorine, citric acid Group, carbonic acid group, benzoic acid group, acetic acid group, ammonium group and the like.
  • the magnesium content of the porous molded body according to the present invention is 10 to 50 wt% as magnesium atoms. If it is less than 10 wt%, the BET specific surface area becomes small and it is not porous. Moreover, when it exceeds 50 wt%, mechanical strength becomes low.
  • the preferred magnesium content is 15 wt% to 45 wt%, more preferably 20 wt% to 40 wt%.
  • the aluminum content of the porous molded body according to the present invention is 5 to 35 wt% as aluminum atoms. If it is less than 5 wt%, the mechanical strength is low. On the other hand, when it exceeds 35 wt%, the BET specific surface area becomes small and it is not porous.
  • the aluminum content is preferably 8 to 35 wt%, more preferably 10 to 30 wt%.
  • the magnesium atom ratio exceeds the above range, it is difficult to easily obtain a molded article having sufficient strength, and when it is less than the above range, it is difficult to obtain the characteristics as a porous body.
  • the pore volume of the porous molded body according to the present invention is 0.01 to 0.5 cm 3 / g.
  • the pore volume of the porous molded body is less than 0.01 cm 3 / g, it cannot be said that it has a sufficient pore volume as a carrier. If it exceeds 0.5 cm 3 / g, the active species metal cannot be sufficiently dispersed and supported when used as a catalyst carrier.
  • a method of obtaining said pore volume using layered double hydroxide particle
  • the average pore diameter of the porous molded body according to the present invention is 300 mm or less.
  • the average pore diameter of the porous molded body exceeds 300 mm, the active species metal cannot be sufficiently dispersed and supported when used as a catalyst carrier.
  • the average pore diameter is preferably 20 to 280 mm, more preferably 50 to 250 mm.
  • a method of obtaining said average pore diameter using layered double hydroxide particle
  • the BET specific surface area of the porous molded body according to the present invention is preferably 10 to 100 m 2 / g.
  • the BET specific surface area is less than 10 m 2 / g, the average pore diameter becomes large, and the active species metal cannot be sufficiently dispersed and supported when used as a catalyst carrier. Those exceeding 100 m 2 / g are not realistic because they cannot be industrially produced. It is preferably 15 to 90 m 2 / g, more preferably 20 to 80 m 2 / g.
  • the average crushing strength of the porous molded body according to the present invention is 3 kg or more. If the average crushing strength is less than 3 kg, it will crack when used at high temperatures.
  • the amount is preferably 4 to 50 kg, more preferably 5 to 40 kg.
  • the method for producing a porous molded body in the present invention can be obtained by preparing a molded body of hydrotalcite compound powder containing magnesium and aluminum as precursors and then heat-treating it in a temperature range of 500 ° C to 1500 ° C. .
  • the hydrotalcite compound powder containing magnesium and aluminum comprises mixing an alkaline aqueous solution containing anions, a magnesium raw material, and an aluminum salt aqueous solution, and a mixed solution having a pH value in the range of 7.0 to 13.0. After that, the mixed solution can be aged in the temperature range of 50 to 300 ° C., then separated by filtration and dried.
  • the aging time is not particularly limited, but is 1 to 80 hours, preferably 3 to 24 hours, more preferably 5 to 18 hours. Growth reactions over 80 hours are not industrial.
  • Magnesium and aluminum salts are not particularly limited as long as they are water-soluble such as nitrates.
  • magnesium raw material magnesium oxide, magnesium hydroxide, magnesium oxalate, magnesium sulfate, magnesium sulfite, magnesium nitrate, magnesium chloride, magnesium citrate, basic magnesium carbonate, magnesium benzoate and the like can be used.
  • aluminum raw material aluminum oxide, aluminum hydroxide, aluminum acetate, aluminum chloride, aluminum nitrate, aluminum oxalate, basic ammonium aluminum, or the like can be used.
  • the average plate surface diameter is preferably 0.05 to 0.4 ⁇ m.
  • the average plate surface diameter is less than 0.05 ⁇ m, it is difficult to filter and wash and industrial production is difficult.
  • it exceeds 0.4 ⁇ m it is difficult to produce a porous molded body. is there.
  • the crystallite size D006 of the hydrotalcite compound powder in the present invention is preferably 0.001 to 0.08 ⁇ m.
  • the crystallite size D006 is less than 0.001 ⁇ m, the viscosity of the aqueous suspension is very high and industrial production is difficult, and when it exceeds 0.08 ⁇ m, it is difficult to produce a catalyst compact. is there. More preferably, it is 0.002 to 0.07 ⁇ m.
  • the BET specific surface area value of the hydrotalcite compound powder containing magnesium and aluminum in the present invention is preferably 3.0 to 300 m 2 / g.
  • the specific surface area value is less than 3.0 m 2 / g, it is difficult to produce a porous molded body, and when it exceeds 300 m 2 / g, the viscosity of the aqueous suspension is very high, Moreover, it is difficult to filter and wash, making it difficult to produce industrially. More preferably, it is 5.0 to 250 m 2 / g.
  • the secondary agglomerated particle size of the hydrotalcite compound powder is 0.1 to 200 ⁇ m.
  • the thickness is preferably 0.2 to 100 ⁇ m.
  • the pulverization treatment can be performed using a general pulverizer (such as an atomizer, Yariya, Henschel mixer).
  • a general pulverizer such as an atomizer, Yariya, Henschel mixer.
  • the hydrotalcite compound powder containing at least magnesium and aluminum which are precursors of the porous molded body, is added with a molding aid, a binder, and water as a dispersion medium, if necessary.
  • a molding aid e.g., a kneader, a kneader or the like
  • water e.g., water
  • an alcohol is added, and after clay-kneading with a kneader (screw kneader or the like), the molding is performed.
  • the molding method can be compression molding, press molding, or tableting.
  • the shape of the molded body of the porous molded body according to the present invention is not particularly limited as long as it is a shape adopted for a normal catalyst.
  • a spherical shape, a cylindrical shape, a hollow cylindrical shape, a pellet shape, and the like is a shape adopted for a normal catalyst.
  • a spherical shape, a cylindrical shape, a hollow cylindrical shape, a pellet shape, and the like is a shape adopted for a normal catalyst.
  • the size of the molded body is usually 1 to 10 mm ⁇ , preferably 2 to 8 mm ⁇ .
  • the clay-like kneaded product formed by the above method can be dried by a method such as natural drying, hot air drying, or vacuum drying.
  • the porous molded body according to the present invention can be obtained by heat-treating the dried clay kneaded product.
  • the heat treatment is performed at 500 ° C to 1500 ° C.
  • the heat treatment temperature is less than 500 ° C., a long heat treatment is required to maintain the crushing strength, which is not industrial.
  • the pore of a porous molded object will be crushed.
  • the temperature is preferably 500 ° C to 1400 ° C, more preferably 600 ° C to 1300 ° C.
  • the heat treatment time is 1 to 72 hours. In the case of less than 1 hour, the crushing strength is reduced, and in the case of exceeding 72 hours, the pores of the porous molded body are crushed and the heat treatment for a long time is not industrial.
  • the time is preferably 2 to 60 hours, more preferably 3 to 50 hours.
  • Molding aids include fatty acids, cellulose, polyvinyl alcohol, starch, methylcellulose, carboxymethylcellulose and the like.
  • the amount added is, for example, 1 to 50 parts by weight with respect to 100 parts by weight of the hydrotalcite compound powder containing magnesium and aluminum.
  • alcohols examples include monohydric alcohols such as ethanol and propanol, glycols such as ethylene glycol, propylene glycol, butanediol and polyethylene glycol, and polyhydric alcohols such as glycerin.
  • the addition amount is, for example, 50 to 150 parts by weight with respect to 100 parts by weight of hydrotalcite compound powder containing magnesium and aluminum.
  • combustible substances wood chips, cork granules, coal powder, activated carbon, crystalline cellulose powder, starch, sucrose, gluconic acid, polyethylene glycol, polyvinyl alcohol, polyacrylamide, polyethylene, polystyrene, etc. and mixtures thereof are added. Also good. As the amount of the combustion substance added increases, the pore volume increases. However, if the amount is excessively added, the strength decreases, so the amount of addition may be adjusted in consideration of the strength.
  • a method may be freely selected as necessary.
  • the porous molded body according to the present invention is fired with a precursor of hydrotalcite, which is a layered double hydroxide, to produce a porous molded body, moisture in the hydrotalcite is dehydrated by firing. Since the oxide is composed of magnesium and aluminum containing a large amount of fine pores, the specific surface area and pore volume are very large. Further, since pores are formed by the absence of moisture, carbonate ions, etc. between the layers of hydrotalcite by firing, the pore diameter can be reduced.
  • the porous molded body according to the present invention can maintain a high specific surface area even when fired at a high temperature, so that the mechanical strength can be increased by sintering at a high temperature. As a result, a porous molded body having a large pore volume and excellent mechanical strength was obtained.
  • the porous molded body obtained by the present invention exhibits a high specific surface area and strength even when kept at a high temperature, a steam reforming catalyst used at a high temperature, a catalyst for producing dimethyl ether by dehydrating methanol, a CO shift catalyst, In a catalyst such as a CO selective oxidation catalyst and a methanation catalyst, it is useful as a catalyst carrier for supporting a catalyst component.
  • the porous molded body magnesium since it contains a large amount of the porous molded body magnesium according to the present invention, it is suitable as a catalyst carrier for reforming hydrocarbons such as city gas and LPG containing a large amount of sulfur components.
  • the porous molded body according to the present invention is a porous molded body having both a specific surface area and mechanical properties, and is suitable for a filter, a desiccant, an adsorbent, a purification agent, a deodorant, a catalyst carrier, and the like. .
  • a typical embodiment of the present invention is as follows.
  • the contents of magnesium and aluminum were obtained by dissolving a sample with an acid and analyzing it using a plasma emission spectroscopic analyzer (Seiko Electronics Co., Ltd., SPS4000).
  • a value was obtained from an average of 100 using a digital force gauge.
  • BET specific surface area value is B. E. T.A. Measured by the method.
  • the average pore diameter and pore volume were determined by BJH method using TriStar 3000 manufactured by Shimadzu Corporation.
  • Example 1 ⁇ Preparation of hydrotalcite compound powder> 4224.2 g of MgSO 4 ⁇ 7H 2 O and 1666.9 g of Al 2 (SO 4 ) 3 ⁇ 8H 2 O were dissolved in pure water to make 15000 ml. Separately, 25,000 ml of an alkali mixed solution was prepared by combining 6776 ml of NaOH (14 mol / L concentration) and 508.8 g of Na 2 CO 3 . The mixed solution of the magnesium salt and aluminum salt was added to the alkali mixed solution, and aging was performed at 80 ° C. for 8 hours to obtain a hydrated double hydroxide. This was separated by filtration, dried and pulverized to obtain hydrotalcite compound powder. The obtained hydrotalcite compound powder had a BET specific surface area of 45.2 m 2 / g. The average particle size of the secondary aggregated particles after the pulverization treatment was 10.5 ⁇ m.
  • the kneaded clay-like kneaded product was formed into a spherical shape by a compression molding method, dried at 120 ° C., and heat-treated at 1100 ° C. for 5 hours.
  • the size of the obtained porous molded body was 5 mm ⁇ , the BET specific surface area was 42.5 m 2 / g, the average pore diameter was 175 mm, and the pore volume was 0.152 cm 3 / g.
  • the Mg content was 30.66 wt%, and the Al content was 26.01 wt%.
  • the average crushing strength was 35.4 kg.
  • Example 2 Mg (NO 3 ) 2 ⁇ 6H 2 O 2884.6 g and Al (NO 3 ) 3 ⁇ 9H 2 O 2110.1 g were dissolved in pure water to make 10,000 ml. Separately, a mixed solution of 20000 ml of alkali was prepared by combining 4032 ml of NaOH (14 mol / L concentration) and 834.8 g of Na 2 CO 3 . A mixed solution of the magnesium salt and aluminum salt was added to the alkali mixed solution, and aging was performed at 60 ° C. for 6 hours to obtain a hydrated double hydroxide. This was separated by filtration, dried and pulverized to obtain hydrotalcite compound powder. The BET specific surface area of the obtained hydrotalcite compound powder was 105.2 m 2 / g. The average particle size of the secondary aggregated particles after the pulverization treatment was 35.2 ⁇ m.
  • Example 3 MgCl 2 ⁇ 6H 2 O 1488.3 g and AlCl 3 ⁇ 9H 2 O 178.5 g were dissolved in pure water to make 8000 ml. Separately, 12,000 ml of an alkali mixed solution was prepared by combining 6077 ml of NaOH (14 mol / L concentration) and 109.7 g of Na 2 CO 3 dissolved therein. A mixed solution of the magnesium salt and aluminum salt was added to the alkali mixed solution, and aging was performed at 160 ° C. for 8 hours to obtain a hydrated double hydroxide. This was separated by filtration, dried and pulverized to obtain hydrotalcite compound powder. The obtained hydrotalcite compound powder had a BET specific surface area of 15.2 m 2 / g. The average particle size of the secondary aggregated particles after the pulverization treatment was 25.2 ⁇ m.
  • hydrotalcite compound powder 665.5 g was mixed with 59.23 g of talc and 62.89 g of starch, further 146.4 g of water and 432.6 g of ethylene glycol, and kneaded with a screw kneader for 0.5 hour.
  • the kneaded clay-like kneaded product was formed into a spherical shape by press molding, dried at 120 ° C., and heat-treated at 1300 ° C. for 10 hours.
  • the obtained porous molded body has a size of 2.2 mm ⁇ , a BET specific surface area of 12.2 m 2 / g, an average pore diameter of 252.4 mm, and a pore volume of 0.025 cm 3 / g. Met.
  • the Mg content was 44.34 wt%
  • the Al content was 9.348 wt%.
  • the average crushing strength was 49.6 kg.
  • Example 4 6251.9 g of MgSO 4 ⁇ 7H 2 O and 2924.8 g of Al 2 (SO 4 ) 3 ⁇ 8H 2 O were dissolved in pure water to make 18000 ml. Separately, 17000 ml of an alkali mixed solution in which 8359 ml of NaOH (14 mol / L concentration) and 892.7 g of Na 2 CO 3 were dissolved was prepared. The mixed solution of the magnesium salt and the aluminum salt was added to the alkali mixed solution and aged at 95 ° C. for 5 hours to obtain a hydrated double hydroxide. This was separated by filtration, dried and pulverized to obtain hydrotalcite compound powder. The obtained hydrotalcite compound powder had a BET specific surface area of 72.1 m 2 / g. The average particle size of the secondary aggregated particles after the pulverization treatment was 7.6 ⁇ m.
  • 2911 g of the obtained hydrotalcite compound powder was mixed with 291.2 g of ⁇ -alumina, 173.2 g of PVA, 960.8 g of water and 2183.8 g of glycerin, and kneaded with a screw kneader for 3.5 hours.
  • the kneaded clay-like kneaded product was formed into a spherical shape by a compression molding method, dried at 120 ° C., and heat-treated at 1050 ° C. for 15 hours.
  • the size of the obtained porous molded body was 8.2 mm ⁇ , the BET specific surface area was 68.2 m 2 / g, the average pore diameter was 125 mm, and the pore volume was 0.224 cm 3 / g. It was.
  • the Mg content was 32.63 wt%, and the Al content was 24.27 wt%.
  • the average crushing strength was 11.25 kg.
  • Comparative Example 1 825.2 g of MgO, 10.52 g of ⁇ -alumina, 124.3 g of PVA, and 436.8 g of water were mixed and kneaded with a screw kneader for 2 hours.
  • the kneaded clay kneaded product was formed into a spherical shape by a compression molding method, dried at 120 ° C., and heat-treated at 1250 ° C. for 4 hours.
  • the size of the obtained molded body was 3.5 mm ⁇ , the BET specific surface area was 2.2 m 2 / g, the average pore diameter was 342 mm, and the pore volume was 0.012 cm 3 / g.
  • the magnesium content was 59.41 wt% and the aluminum content was 0.785 wt%. Furthermore, the average crushing strength was 4.15 kg.
  • Comparative Example 2 A mixture of 1231.2 g of ⁇ -alumina and 59.61 g of PVA was granulated while spraying pure water with a rolling granulator to obtain a spherical ⁇ -alumina compact.
  • the obtained molded body was dried at 120 ° C. and heat-treated at 850 ° C. for 10 hours.
  • the obtained molded body had a size of 2.2 mm ⁇ , a BET specific surface area of 185.5 m 2 / g, an average pore diameter of 54.2 mm, and a pore volume of 0.512 cm 3 / g. .
  • the aluminum content was 51.9 wt%. Further, the average crushing strength was 0.8 kg.
  • Comparative Example 3 1142 g of water was mixed with 1512 g of the hydrotalcite powder produced in Example 1, and kneaded with a screw kneader for 1 hour.
  • the kneaded clay-like kneaded product was formed into a spherical shape by a compression molding method, dried at 120 ° C., and heat-treated at 1100 ° C. for 5 hours.
  • the size of the obtained porous molded body was 5 mm ⁇
  • the BET specific surface area was 52.4 m 2 / g
  • the average pore diameter was 142 mm
  • the pore volume was 0.182 cm 3 / g.
  • the Mg content was 40.03 wt%
  • the Al content was 17.78 wt%.
  • the average crushing strength was 0.2 kg.
  • Table 1 shows the properties of the obtained porous molded body.
  • Ni was supported as a catalytically active component on the porous molded body obtained in Example 1, and the catalyst was evaluated by a steam reforming reaction.
  • Ni support was supported by an impregnation method using nickel nitrate, followed by calcination and reduction treatment to obtain a steam reforming reaction catalyst.
  • the Ni content in the Ni-supporting porous molded body was 17.2 wt%, and the size of the metal Ni fine particles was 3 nm.
  • Methane gas and water vapor were passed through this catalyst tube (reactor) at a reaction temperature of 300 ° C. to 700 ° C. and a space velocity of 3000 h ⁇ 1 to carry out a steam reforming reaction.
  • Table 2 shows the reaction temperature (from 300 ° C. to 300 ° C. under reaction conditions using pure methane gas as a raw material gas and GHSV of 3000 h ⁇ 1 and 10000 h ⁇ 1 , water vapor / carbon (S / C) of 3.0, and reaction time of 24 h. 700 ° C.) and the C1 conversion rate.
  • Ni was supported as a catalyst active component on the molded body obtained in Comparative Example 1, and the catalyst was evaluated by a steam reforming reaction.
  • Ni support was supported by an impregnation method using nickel nitrate, followed by calcination and reduction treatment to obtain a steam reforming reaction catalyst.
  • the Ni content in the Ni-supported molded body was 17.6 wt%, and the size of the metal Ni fine particles was 38 nm.
  • Ni was supported as a catalyst active component on the molded body obtained in Comparative Example 3, and the catalyst was evaluated by a steam reforming reaction.
  • Ni support was supported by an impregnation method using nickel nitrate, followed by calcination and reduction treatment to obtain a steam reforming reaction catalyst.
  • the Ni content in the Ni-supported molded body was 16.7 wt%, and the size of the metal Ni fine particles was 8 nm. After the catalyst evaluation, the molded body was cracked and pulverized.
  • the catalyst using the porous molded body according to the present invention has a high conversion rate and can maintain a high mechanical strength.
  • the porous molded body according to the present invention is composed of at least magnesium and aluminum and has excellent mechanical strength while having a large BET specific surface area and pore volume. Therefore, since the porous molded body according to the present invention is a porous molded body having both a specific surface area and mechanical properties, it is suitable for a filter, a desiccant, an adsorbent, a purifying agent, a deodorant or a catalyst carrier. It is.

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Abstract

比表面積及び機械的特性を両立させた多孔質成形体であって、フィルター、乾燥剤、吸着剤、精製剤、消臭剤、触媒担体等に好適に利用することが可能な、微小な気孔を多量に含み、高い比表面積を有し、しかも、高い強度を有するマグネシウム及びアルミニウムからなる多孔質成形体及びその製造方法の提供を目的とする。 　少なくともマグネシウム及びアルミニウムからなる多孔質成形体であって、マグネシウムをマグネシウム原子としてを１０～５０ｗｔ％、アルミニウムをアルミニウム原子として５～３５ｗｔ％含有し、細孔容積が０．０１～０．５ｃｍ３／ｇであって平均細孔径が３００Å以下であり、平均圧壊強度が３ｋｇ以上であることを特徴とする多孔質成形体は、少なくともマグネシウム及びアルミニウムを含有したハイドロタルサイトを成形し、５００°C～１５００°Cの範囲で焼成して得ることができる。

Description

多孔質成形体及びその製造方法、並びに触媒用担体及び触媒
　本発明は、少なくともマグネシウム及びアルミニウムからなる多孔質成形体及びその製造方法に関するものであり、更に詳しくは、比表面積及び機械的特性を両立させた多孔質成形体であって、フィルター、乾燥剤、吸着剤、精製剤、消臭剤、触媒担体等に好適に利用することが可能な、微小な気孔を多量に含み、高い比表面積を有し、しかも、高い強度を有するマグネシウム及びアルミニウムからなる多孔質成形体、及びその製造方法の提供を目的とする。
　本発明は、工業的に大量に生産可能な耐硫黄被毒性に優れたマグネシウムとアルミニウムからなる多孔質成形体の提供を目的とする。
　従来から、セラミックス多孔体は、耐熱性、耐衝撃性、耐薬品性、常温及び高温における強度特性、軽量性などに優れるため、各種フィルター（ガス分離、固体分離、除菌、除塵等）、乾燥剤、吸着剤、精製剤、消臭剤、触媒担体、吸音材、断熱材又はセンサー等として広く利用され、不可欠な工業材料となっている。
　これらの用途に使用される場合、セラミックス多孔体の細孔分布や細孔容積に対する要求は様々である。例えば、触媒担体として利用される場合、担持成分が大量に担持できるように高細孔容積が必要とされる。さらに、触媒担体や吸着剤として固定床設備で利用する場合、触媒の抜き取りや充填時の圧壊が起こり難い高強度が必要であり、これら両機能を有する高細孔容積、且つ、高強度であるセラミックス成形体が要求される。
　しかし、最近では、フィルターや触媒担体等の用途において、より大きな比表面積、より高い強度、より優れた耐熱性が要求され、従来のセラミックス多孔体では、これらの要求を満たすことは困難になりつつある。各種フィルターや触媒担体として利用されているアルミナ多孔体は、主にγ―アルミナであるが、γ―アルミナは１０００℃付近で安定相のα―アルミナへ相転移し、比表面積が著しく低下し、触媒担体としての機能を失ってしまう問題点があった。
　一般的なアルミナ系成形体、マグネシア成形体の報告がある（特許文献１～４）。
特開２００３－４８７６８号公報 特開２００７－１１７９１６号公報 特開２００４－１６８６２９号公報 特開２００３－２８４９４９号公報
　前記特許文献１には、α―アルミナ成形体について記載されており、機械的強度が高い成形体であるが、ＢＥＴ比表面積が小さい。
　前記特許文献２及び３では、アルミナ成形体について記載されており、細孔容積、ＢＥＴ比表面積は大きいが、機械的強度が弱い。
　前記特許文献４ではマグネシアを圧縮成形法により高強度な成形体としているが、ＢＥＴ比表面積や細孔容積等の記載はないが、小さいと容易に推測される。
　一般的に用いられるセラミックス多孔体としてα―アルミナの成形体があるが、高温焼成により焼結することで圧壊強度を高くするため、比表面積値が小さい。
　また、γ―アルミナやα―アルミナ、シリカ、ゼオライト等の成形体については多数報告されているが、マグネシウムを多量に含み、且つ、大きな比表面積を持ち、高い圧壊強度を有する多孔質成形体の報告はない。
　また、ハイドロタルサイトを前駆体として、成形体を作製する方法についてはこれまでに報告はない。
　また、多孔質粉末の圧粉成形体について種々の報告があるが、機械的強度が不十分であったり、成形可能な形状が限られるほか、粉末の脱落などによる損傷を生じやすい等の難点を有する。
　また、無機結合材を配合して行う焼結体の製造においては、無機結合剤が多孔質粉末粒子の細孔を塞ぐことによる性能低下を付随し、機械的強度を高めるべく多量添加すると重量増のみならず多孔構造の性能低下が大きくなるという問題がある。さらに焼結については、強度面から高温処理を必要とするため、多孔質粉末粒子の結晶構造の変質により細孔及び比表面積が損なわれ、しかも熱エネルギーコストの負担増を余儀なくされる
　そこで、本発明では、少なくともマグネシウム及びアルミニウムからなる多孔質成形体及びその製造方法に関するものであり、更に詳しくは、比表面積及び機械的特性を両立させた多孔質成形体であって、フィルター、乾燥剤、吸着剤、精製剤、消臭剤、触媒担体等に好適に利用することが可能な、微小な気孔を多量に含み、高い比表面積を有し、しかも、高い強度を有するマグネシウム及びアルミニウムからなる多孔質成形体、及びその製造方法の提供を目的とする。
　また、本発明は、工業的に大量に生産可能な耐硫黄被毒性に優れたマグネシウムとアルミニウムからなる多孔質成形体の提供を目的とする。
　前記技術的課題は、次の通りの本発明によって達成できる。
　即ち、本発明は、少なくともマグネシウム及びアルミニウムからなる多孔質成形体であって、マグネシウムをマグネシウム原子として１０～５０ｗｔ％、アルミニウムをアルミニウム原子として５～３５ｗｔ％含有し、細孔容積が０．０１～０．５ｃｍ３／ｇであって平均細孔径が３００Å以下であり、平均圧壊強度が３ｋｇ以上であることを特徴とする多孔質成形体である（本発明１）。
　また、本発明は、ＢＥＴ比表面積が１０～１００ｍ２／ｇである前記多孔質成形体である（本発明２）。
また、本発明は、マグネシウム及びアルミニウムを含有したハイドロタルサイトを成形し、５００℃～１５００℃の範囲で焼成して形成される前記多孔質成形体である（本発明３）。
　また、本発明は、本発明１～３のいずれかに記載の多孔質成形体を用いた触媒用担体である（本発明４）。
　また、本発明は、本発明１～３のいずれかに記載の多孔質成形体を用いた触媒である（本発明５）。
　本発明に係る多孔質成形体は、少なくともマグネシウム及びアルミニウムからなり、大きなＢＥＴ比表面積及び細孔容積を有しながら、機械的強度にも優れているものである。
　本発明に係る多孔質成形体は、比表面積及び機械的特性を両立させた多孔質成形体であって、フィルター、乾燥剤、吸着剤、精製剤、消臭剤又は触媒担体等に好適である。
　本発明により得られる多孔質成形体は、高温に保持しても高比表面積と強度を示すので、高温で使用される水蒸気改質触媒、メタノールを脱水してジメチルエーテル製造用触媒、ＣＯシフト触媒、ＣＯ選択酸化触媒、メタネーション触媒などのような触媒において、触媒成分を担持するための触媒担体として有用である。
　また、本発明に係る多孔質成形体はマグネシウムを大量に含んでいるため、硫黄成分を多量に含んでいる都市ガスやＬＰＧ等の炭化水素を改質する触媒の担体として好適である。
　本発明に係る多孔質成形体について述べる。
　本発明に係る多孔質成形体は少なくともマグネシウムとアルミニウムから構成された化合物である。アルミニウムとマグネシウム元素の他に特に限定されないが、ナトリウム、カルシウム、ケイ素、鉄、ニッケル、亜鉛などの元素が含まれてもよい。また、他の成分としては、以下の製造方法において説明する熱処理などの後に残存する原料に由来するもの、例えば、酸素、水酸基、シュウ酸基、硫酸基、亜硫酸基、硝酸基、塩素、クエン酸基、炭酸基、安息香酸基、酢酸基、アンモニウム基などが挙げられる。
　本発明に係る多孔質成形体のマグネシウムの含有量は、マグネシウム原子として１０～５０ｗｔ％である。１０ｗｔ％未満の場合はＢＥＴ比表面積が小さくなり多孔質ではなくなる。また、５０ｗｔ％を超える場合は機械的強度が低くなる。好ましいマグネシウムの含有量は１５ｗｔ％～４５ｗｔ％であり、より好ましくは２０ｗｔ％～４０ｗｔ％である。
　また、本発明に係る多孔質成形体のアルミニウムの含有量は、アルミニウム原子として５～３５ｗｔ％である。５ｗｔ％未満の場合には機械的強度が低くなる。また、３５ｗｔ％を超える場合はＢＥＴ比表面積が小さくなり多孔質ではなくなる。好ましいアルミニウムの含有量は８～３５ｗｔ％であり、より好ましくは１０ｗｔ％～３０ｗｔ％である。
　本発明に係る多孔質成形体のマグネシウム原子とアルミニウム原子との比率は特に限定されないが、アルミニウム原子に対してマグネシウム原子が多い方が好ましく、マグネシウム原子とアルミニウム原子のモル比はＭｇ：Ａｌ＝５：１～１：１が好ましい。マグネシウム原子の比率が前記範囲を超える場合には十分な強度を有する成形体を容易に得ることが困難となり、前記範囲未満の場合には多孔質体としての特性が得られ難くなる。
　本発明に係る多孔質成形体の細孔容積は０．０１～０．５ｃｍ３／ｇである。多孔質成形体の細孔容積が０．０１ｃｍ３／ｇ未満の場合、担体として十分な細孔容積を有するものとは言い難い。０．５ｃｍ３／ｇを超える場合、触媒担体として用いる際に活性種金属を十分に分散担持できなくなる。好ましくは０．０２～０．４５ｃｍ３／ｇ、より好ましくは０．０５～０．４０ｃｍ３／ｇである。なお、上記の細孔容積を得る方法としては、例えば、前駆体として層状複水水酸化物粒子及び燃焼性物質を用いること、さらに焼成条件を調整することが挙げられる。
　本発明に係る多孔質成形体の平均細孔径は３００Å以下である。多孔質成形体の平均細孔径が３００Åを超える場合、触媒担体として用いる際に活性種金属を十分に分散担持できなくなる。平均細孔径は好ましくは２０～２８０Å、より好ましくは５０～２５０Åである。なお、上記の平均細孔径を得る方法としては、例えば、前駆体として層状複水水酸化物粒子及び燃焼性物質を用いること、さらに焼成条件を調整することが挙げられる。
　本発明に係る多孔質成形体のＢＥＴ比表面積は１０～１００ｍ２／ｇが好ましい。ＢＥＴ比表面積が１０ｍ２／ｇ未満の場合には、平均細孔径が大きくなり、触媒担体として用いる際に活性種金属を十分に分散担持できなくなる。１００ｍ２／ｇを超えたものは工業的な生産ができないため現実的ではない。好ましくは１５～９０ｍ２／ｇ、より好ましくは２０～８０ｍ２／ｇである。
　本発明に係る多孔質成形体の平均圧壊強度は３ｋｇ以上である。平均圧壊強度が３ｋｇ未満の場合には、高温で使用される際に割れてしまう。好ましくは４～５０ｋｇ、より好ましくは５～４０ｋｇである。
　本発明に係る多孔質成形体の製造方法について述べる。
　本発明における多孔質成形体の製造方法は、前駆体としてマグネシウム及びアルミニウムを含有するハイドロタルサイト化合物粉末の成形体を作製した後、５００℃～１５００℃の温度範囲で熱処理して得ることができる。
　本発明に係るマグネシウム及びアルミニウムを含有するハイドロタルサイト化合物粉末は、アニオンを含有したアルカリ性水溶液とマグネシウム原料とアルミニウム塩水溶液を混合し、ｐＨ値が７．０～１３．０の範囲の混合溶液とした後、該混合溶液を５０～３００℃の温度範囲で熟成し、その後、濾別分離し、乾燥して得ることができる。
　熟成時間は特に限定されるものではないが、１～８０時間、好ましくは、３～２４時間、より好ましくは、５～１８時間である。８０時間を超える成長反応は工業的ではない。
　マグネシウム、アルミニウム塩としては硝酸塩など水溶性のものであれば特に限定しない。
　マグネシウム原料としては、酸化マグネシウム、水酸化マグネシウム、シュウ酸マグネシウム、硫酸マグネシウム、亜硫酸マグネシウム、硝酸マグネシウム、塩化マグネシウム、クエン酸マグネシウム、塩基性炭酸マグネシウム、安息香酸マグネシウム等を用いることができる。
　アルミニウム原料としては、酸化アルミニウム、水酸化アルミニウム、酢酸アルミニウム、塩化アルミニウム、硝酸アルミニウム、シュウ酸アルミニウム、塩基性アンモニウムアルミニウム等を用いることができる。
　本発明に係る多孔質成形体の前駆体であるマグネシウム及びアルミニウムを含有するハイドロタルサイト化合物粉末の粒子における平均板面径は０．０５～０．４μｍが好ましい。平均板面径が０．０５μｍ未満の場合には、濾別・水洗が困難となり工業的な生産が困難であり、０．４μｍを超える場合には、多孔質成形体を作製することが困難である。
　本発明におけるハイドロタルサイト化合物粉末の結晶子サイズＤ００６は０．００１～０．０８μｍが好ましい。結晶子サイズＤ００６が０．００１μｍ未満の場合には、水性懸濁液の粘度が非常に高く工業的な生産が難しく、０．０８μｍを超える場合には、触媒成形体を作製するのが困難である。より好ましくは０．００２～０．０７μｍである。
　本発明におけるマグネシウム及びアルミニウムを含有するハイドロタルサイト化合物粉末のＢＥＴ比表面積値は３．０～３００ｍ２／ｇが好ましい。比表面積値が３．０ｍ２／ｇ未満の場合には、多孔質成形体を作製するのが困難であり、３００ｍ２／ｇを超える場合には、水性懸濁液の粘度が非常に高く、また濾別・水洗が困難となり工業的に生産が困難である。より好ましくは５．０～２５０ｍ２／ｇである。
　本発明におけるマグネシウム及びアルミニウムを含有するハイドロタルサイトのマグネシウム原子とアルミニウム原子との比率は特に限定されないが、マグネシウム原子とアルミニウム原子のモル比はＭｇ：Ａｌ＝４：１～１：１がより好ましい。
　ハイドロタルサイト化合物粉末の二次凝集粒子径は０．１～２００μｍである。０．１μｍ未満の場合には粉砕処理が困難となり工業的に生産が困難である。２００μｍ超える場合には成形体を作製することが困難である。好ましくは０．２～１００μｍである。
　粉砕処理は一般的な粉砕装置（アトマイザー、ヤリヤ、ヘンシェルミキサー等）を用いて行うことができる。
　本発明に係る多孔質成形体の成形では、多孔質成形体の前駆体である少なくともマグネシウム及びアルミニウムを含有するハイドロタルサイト化合物粉末に、必要により、成形助剤、結合剤、さらに分散媒体として水又はアルコールを添加し、混練機（スクリューニーダーなど）で粘土状混練としたのちに成形する。成形する方法には、圧縮成形、プレス成形、打錠成形で行うことができる。
　本発明に係る多孔質成形体の成形体の形状は、特に制約されず、通常の触媒に採用されている形状であれば良い。例えば、球状、円柱状、中空円柱状、ペレット状等である。
　球状の場合、その成形体のサイズは、通常１～１０ｍｍφであり、好ましくは２～８ｍｍφである。
　前記方法により成形した粘土状混練物の乾燥は、自然乾燥、熱風乾燥、真空乾燥などの方法により乾燥することができる。
　さらに乾燥した粘土状混練物を熱処理することにより本発明に係る多孔質成形体を得ることができる。熱処理は５００℃～１５００℃である。熱処理温度が５００℃未満の場合には圧壊強度を保つため長時間の熱処理が必要となり、工業的ではない。また１５００℃を超える場合には、多孔質成形体の細孔が潰れてしまう。好ましくは５００℃～１４００℃、より好ましくは６００℃～１３００℃である。
　熱処理の時間は１～７２時間である。１時間未満の場合では圧壊強度が低下し、７２時間を超える場合は、多孔質成形体の細孔が潰れてしまう上に、長時間の熱処理は工業的ではない。好ましくは２～６０時間であり、より好ましくは３～５０時間である。
　成形助剤には脂肪酸、セルロース、ポリビニルアルコール、でんぷん、メチルセルロース、カルボキシメチルセルロース等が挙げられる。焼成処理により、燃焼消失し多孔質成形体には残留しない。添加量はマグネシウム及びアルミニウムを含有するハイドロタルサイト化合物粉末１００重量部に対して、例えば１～５０重量部である。
　結合剤には再水和性のないアルミナ、αーアルミナ、アルミニウム塩、シリカ、粘土、タルク、ベントナイト、ゼオライト、コージェライト、チタニアアルカリ金属塩、アルカリ土類金属塩、希土類金属塩、ジルコニア、ムライト、セピオライト、モンモリロナイト、ハロサイト、サポライト、スチブンサイト、ヘクトライト、シリカアルミナなどがある。酸化物以外の塩を添加した場合は、焼成で塩が分解し酸化物となることが重要である。添加量はマグネシウム及びアルミニウムを含有するハイドロタルサイト化合物粉末１００重量部に対して、例えば１～５０重量部である。
　アルコール類としては、例えばエタノール、プロパノールなどの１価アルコール類、エチレングリコール、プロピレングリコール、ブタンジオール、ポリエチレングリコールなどのグリコール類、グリセリンなどの多価アルコール類等が上げられる。添加量はマグネシウム及びアルミニウムを含有するハイドロタルサイト化合物粉末１００重両部に対して、例えば５０～１５０重量部である。
　また、燃焼性物質として、木屑、コルク粒、石炭末、活性炭、結晶性セルロース粉末、でんぷん、蔗糖、グルコン酸、ポリエチレングリコール、ポリビニルアルコール、ポリアクリルアミド、ポリエチレン、ポリスチレン等及びこれらの混合物を添加しても良い。前記燃焼物質の添加量が多いほど細孔容積が大きくなるが、添加しすぎると強度低下を起こすので強度を考慮して添加量の調整を行えばよい。
　別にハニカム状とする場合には、必要に応じて自由に手法を選択すればよい。
＜作用＞
　本発明に係る多孔質成形体が高い比表面積を有し、且つ、優れた機械的強度を有する理由については、本発明者は次のように推定している。
　本発明に係る多孔質成形体は、層状複水酸化物であるハイドロタルサイトを成形したものを前駆体として焼成して多孔質成形体を作製するため、焼成によりハイドロタルサイト中の水分が脱水され微細な細孔を大量に含むマグネシウムとアルミニウムからなる酸化物となるため、比表面積、細孔容量が非常に大きい。また、焼成によりハイドロタルサイトの層間の水分や炭酸イオン等が無くなることにより、細孔が形成されるため、細孔径は小さくできる。
　本発明に係る多孔質成形体は、前記理由により、高温で焼成しても高比表面積を維持することができるため、高温での焼結により機械的強度を高くすることができる。その結果、大きな細孔容積を有し、しかも、機械的強度に優れる多孔質成形体が得られた。
　本発明により得られる多孔質成形体は、高温に保持しても高比表面積と強度を示すので、高温で使用される水蒸気改質触媒、メタノールを脱水してジメチルエーテル製造用触媒、ＣＯシフト触媒、ＣＯ選択酸化触媒、メタネーション触媒などのような触媒において、触媒成分を担持するための触媒担体として有用である。
　また、本発明に係る多孔質成形体マグネシウムを大量に含んでいるため、硫黄成分を多量に含んでいる都市ガスやＬＰＧ等の炭化水素を改質する触媒の担体として好適である。
　本発明に係る多孔質成形体は、比表面積及び機械的特性を両立させた多孔質成形体であって、フィルター、乾燥剤、吸着剤、精製剤、消臭剤、触媒担体等に好適である。
　本発明の代表的な実施の形態は次の通りである。
　マグネシウム及びアルミニウムの含有量は、試料を酸で溶解し、プラズマ発光分光分析装置（セイコー電子工業（株）、ＳＰＳ４０００）を用い分析して求めた。
　触媒成形体の強度測定には、デジタルフォースゲージを用い１００個の平均から値を求めた。
　ＢＥＴ比表面積値は、窒素によるＢ．Ｅ．Ｔ．法により測定した。
　平均細孔径及び細孔容積は、島津製作所社製ＴｒｉＳｔａｒ３０００を用いてＢＪＨ法により求めた。
　実施例１　＜ハイドロタルサイト化合物粉末の調整＞：
　ＭｇＳＯ４・７Ｈ２Ｏ　４２２４．２ｇとＡｌ２（ＳＯ４）３・８Ｈ２Ｏ　１６６６．９ｇとを純水で溶解させ１５０００ｍｌとした。別にＮａＯＨ　６７７６ｍｌ（１４ｍｏｌ／Ｌ濃度）とＮａ２ＣＯ３　５０８．８ｇを溶解させたものを合わせた２５０００ｍｌのアルカリ混合溶液を用意した。このアルカリ混合溶液に前記マグネシウム塩とアルミニウム塩との混合溶液を加え、８０℃で８時間熟成を行って含水複水酸化物を得た。これを濾別分離後、乾燥、粉砕しハイドロタルサイト化合物粉末を得た。得られたハイドロタルサイト化合物粉末のＢＥＴ比表面積は４５．２ｍ２／ｇであった。また粉砕処理後の二次凝集粒子の平均粒子径は１０．５μｍであった。
　＜多孔質成形体の調整＞
　得られたハイドロタルサイト化合物粉末　１８１５ｇにベーマイト　３６０．３ｇとＰＶＡ　４４．４７ｇ、さらに水　３５３．９ｇとプロピレングリコール　９２５．７ｇを混合し、スクリューニーダーで１時間混練した。混練後の粘土状混練物を圧縮成形法により球状に成形後、１２０℃で乾燥し、１１００℃で５時間熱処理を行った。得られた多孔質成形体の大きさは５ｍｍφであり、ＢＥＴ比表面積は４２．５ｍ２／ｇであり、平均細孔径は１７５Åであり、細孔容積は０．１５２ｃｍ３／ｇであった。またＭｇ含有量は分析の結果、３０．６６ｗｔ％であり、Ａｌ含有量は２６．０１ｗｔ％であった。さらに平均圧壊強度は３５．４ｋｇであった。
　実施例２：
　Ｍｇ（ＮＯ３）２・６Ｈ２Ｏ　２８８４．６ｇとＡｌ（ＮＯ３）３・９Ｈ２Ｏ　２１１０．１ｇとを純水で溶解させ１００００ｍｌとした。別にＮａＯＨ　４０３２ｍｌ（１４ｍｏｌ／Ｌ濃度）とＮａ２ＣＯ３　８３４．８ｇを溶解させたものを合わせた２００００ｍｌのアルカリ混合溶液を用意した。このアルカリ混合溶液に前記マグネシウム塩とアルミニウム塩との混合溶液を加え、６０℃で６時間熟成を行って含水複水酸化物を得た。これを濾別分離後、乾燥、粉砕しハイドロタルサイト化合物粉末を得た。得られたハイドロタルサイト化合物粉末のＢＥＴ比表面積は１０５．２ｍ２／ｇであった。また粉砕処理後の二次凝集粒子の平均粒子径は３５．２μｍであった。
　得られたハイドロタルサイト化合物粉末　１７０１ｇにカオリナイト　７７４．２ｇとメチルセルロース　３１３．９ｇ、さらに水　５１０．５ｇとエチレングリコール　１５３１．４ｇを混合し、スクリューニーダーで５時間混練した。混練後の粘土状混練物を押出成形により円柱状に成形後、１２０℃で乾燥し、７００℃で１８時間熱処理を行った。得られた多孔質成形体の大きさは３ｍｍφであり、ＢＥＴ比表面積は９８．３ｍ２／ｇであり、平均細孔径は８２．４Åであり、細孔容積は０．４２１ｃｍ３／ｇであった。またＭｇ含有量は分析の結果、１６．１４ｗｔ％であり、Ａｌ含有量は２７．４８ｗｔ％であった。さらに平均圧壊強度は３．６ｋｇであった。
　実施例３：
　ＭｇＣｌ２・６Ｈ２Ｏ　１４８８．３ｇとＡｌＣｌ３・９Ｈ２Ｏ　１７８．５ｇとを純水で溶解させ８０００ｍｌとした。別にＮａＯＨ　６０７７ｍｌ（１４ｍｏｌ／Ｌ濃度）とＮａ２ＣＯ３　１０９．７ｇを溶解させたものを合わせた１２０００ｍｌのアルカリ混合溶液を用意した。このアルカリ混合溶液に前記マグネシウム塩とアルミニウム塩との混合溶液を加え、１６０℃で８時間熟成を行って含水複水酸化物を得た。これを濾別分離後、乾燥、粉砕しハイドロタルサイト化合物粉末を得た。得られたハイドロタルサイト化合物粉末のＢＥＴ比表面積は１５．２ｍ２／ｇであった。また粉砕処理後の二次凝集粒子の平均粒子径は２５．２μｍであった。
　得られたハイドロタルサイト化合物粉末　６６５．５ｇにタルク　５９．２３ｇとデンプン　６２．８９ｇ、さらに水　１４６．４ｇとエチレングリコール　４３２．６ｇを混合し、スクリューニーダーで０．５時間混練した。混練後の粘土状混練物をプレス成形により球状に成形後、１２０℃で乾燥し、１３００℃で１０時間熱処理を行った。得られた多孔質成形体の大きさは２．２ｍｍφであり、ＢＥＴ比表面積は１２．２ｍ２／ｇであり、平均細孔径は２５２．４Åであり、細孔容積は０．０２５ｃｍ３／ｇであった。またＭｇ含有量は分析の結果、４４．３４ｗｔ％であり、Ａｌ含有量は９．３４８ｗｔ％であった。さらに平均圧壊強度は４９．６ｋｇであった。
　実施例４：
　ＭｇＳＯ４・７Ｈ２Ｏ　６５２１．９ｇとＡｌ２（ＳＯ４）３・８Ｈ２Ｏ　２９２４．８ｇとを純水で溶解させ１８０００ｍｌとした。別にＮａＯＨ　８３５９ｍｌ（１４ｍｏｌ／Ｌ濃度）とＮａ２ＣＯ３　８９２．７ｇを溶解させたものを合わせた１７０００ｍｌのアルカリ混合溶液を用意した。このアルカリ混合溶液に前記マグネシウム塩とアルミニウム塩との混合溶液を加え、９５℃で５時間熟成を行って含水複水酸化物を得た。これを濾別分離後、乾燥、粉砕しハイドロタルサイト化合物粉末を得た。得られたハイドロタルサイト化合物粉末のＢＥＴ比表面積は７２．１ｍ２／ｇであった。また粉砕処理後の二次凝集粒子の平均粒子径は７．６μｍであった。
　得られたハイドロタルサイト化合物粉末　２９１１ｇにγ-アルミナ　２９１．２ｇとＰＶＡ　１７３．２ｇ、さらに水　９６０．８ｇとグリセリン　２１８３．８ｇを混合し、スクリューニーダーで３．５時間混練した。混練後の粘土状混練物を圧縮成形法により球状に成形後、１２０℃で乾燥し、１０５０℃で１５時間熱処理を行った。得られた多孔質成形体の大きさは８．２ｍｍφであり、ＢＥＴ比表面積は６８．２ｍ２／ｇであり、平均細孔径は１２５Åであり、細孔容積は０．２２４ｃｍ３／ｇであった。またＭｇ含有量は分析の結果、３２．６３ｗｔ％であり、Ａｌ含有量は２４．２７ｗｔ％であった。さらに平均圧壊強度は１１．２５ｋｇであった。
　比較例１：
　ＭｇＯ　８２５.２ｇとγ－アルミナ　１０．５２ｇとＰＶＡ　１２４．３ｇと水４３６．８ｇを混合し、スクリューニーダーで２時間混練した。混練後の粘土状混練物を圧縮成形法により球状に成形後、１２０℃で乾燥し、１２５０℃で４時間熱処理を行った。得られた成形体の大きさは３．５ｍｍφであり、ＢＥＴ比表面積は２．２ｍ２／ｇであり、平均細孔径は３４２Åであり、細孔容積は０．０１２ｃｍ３／ｇ。またマグネシウムの含有量は５９．４１ｗｔ％であり、アルミニウムの含有量は０．７８５ｗｔ％であった。さらに平均圧壊強度は４．１５ｋｇであった。
　比較例２：
　γ－アルミナ　１２３１．２ｇにＰＶＡ　５９．６１ｇを混合したものを、転動造粒機にて純水をスプレーしながら造粒し、球状のγ－アルミナ成形体を得た。得られた成形体を１２０℃で乾燥し、８５０℃で１０時間熱処理を行った。得られた成形体の大きさ２．２ｍｍφであり、ＢＥＴ比表面積は１８５．５ｍ２／ｇであり、平均細孔径は５４．２Åであり、細孔容積は０．５１２ｃｍ３／ｇであった。またアルミニウムの含有量は５１．９ｗｔ％であった。さらに平均圧壊強度は０．８ｋｇであった。
　比較例３：
　実施例１で作製したハイドロタルサイト粉末　１５１２ｇに水　１１４２ｇを混合し、スクリューニーダーで１時間混練した。混練後の粘土状混練物を圧縮成形法により球状に成形後、１２０℃で乾燥し、１１００℃で５時間熱処理を行った。得られた多孔質成形体の大きさは５ｍｍφであり、ＢＥＴ比表面積は５２．４ｍ２／ｇであり、平均細孔径は１４２Åであり、細孔容積は０．１８２ｃｍ３／ｇであった。またＭｇ含有量は分析の結果、４０．０３ｗｔ％であり、Ａｌ含有量は１７．７８ｗｔ％であった。さらに平均圧壊強度は０．２ｋｇであった。
　得られた多孔質成形体の諸特性を表１に示す。
Figure JPOXMLDOC01-appb-T000001
　使用例１：
　実施例１で得られた多孔質成形体に触媒活性成分としてＮｉを担持し、水蒸気改質反応による触媒評価を行った。Ｎｉ担持には硝酸ニッケルを用い含浸法にて担持後、焼成、還元処理することにより水蒸気改質反応用触媒とした。Ｎｉ担持多孔質成形体中のＮｉ含有量は１７．２ｗｔ％であり、金属Ｎｉ微粒子の大きさは３ｎｍであった。
＜触媒活性評価＞
　上記Ｎｉ担持多孔質成形体を用いて、水蒸気改質反応での触媒活性評価を行った。触媒を直径２０ｍｍのステンレス製反応管に１０ｃｃ充填して触媒管を作製した。
　この触媒管（反応器）に対して、メタンガス及び水蒸気を、反応温度３００℃～７００℃、空間速度を３０００ｈ－１として流通させ水蒸気改質反応を行った。
　触媒性能の評価には、下記式に示したＣ１転化率を用いた。
Ｃ１転化率＝（ＣＯ＋ＣＯ２）／（ＣＯ＋ＣＯ２＋ＣＨ４）
　表２には、原料ガスとして純メタンガスを用いＧＨＳＶが３０００ｈ－１及び１００００ｈ－１、水蒸気／炭素（Ｓ／Ｃ）が３．０、反応時間が２４ｈの反応条件における、反応温度（３００℃～７００℃）とＣ１転化率との関係を示す。
　使用例２：
　比較例１で得られた成形体に触媒活性成分としてＮｉを担持し、水蒸気改質反応による触媒評価を行った。Ｎｉ担持には硝酸ニッケルを用い含浸法にて担持後、焼成、還元処理することにより水蒸気改質反応用触媒とした。Ｎｉ担持成形体中のＮｉ含有量は１７．６ｗｔ％であり、金属Ｎｉ微粒子の大きさは３８ｎｍであった。
　使用例３：
　比較例３で得られた成形体に触媒活性成分としてＮｉを担持し、水蒸気改質反応による触媒評価を行った。Ｎｉ担持には硝酸ニッケルを用い含浸法にて担持後、焼成、還元処理することにより水蒸気改質反応用触媒とした。Ｎｉ担持成形体中のＮｉ含有量は１６．７ｗｔ％であり、金属Ｎｉ微粒子の大きさは８ｎｍであった。触媒評価後には成形体は割れ、粉化してしまった。
Figure JPOXMLDOC01-appb-T000002
　表２に示すとおり、本発明に係る多孔質成形体を用いた触媒は、高い転化率を有するとともに、高い機械的強度を維持できることが確認された。
　本発明に係る多孔質成形体は少なくともマグネシウム及びアルミニウムからなり、大きなＢＥＴ比表面積及び細孔容積を有しながら、機械的強度に優れている。従って、本発明に係る多孔質成形体は、比表面積及び機械的特性を両立させた多孔質成形体であるので、フィルター、乾燥剤、吸着剤、精製剤、消臭剤又は触媒担体等に好適である。

Claims (5)

  1. 　少なくともマグネシウム及びアルミニウムからなる多孔質成形体であって、マグネシウムをマグネシウム原子として１０～５０ｗｔ％、アルミニウムをアルミニウム原子として５～３５ｗｔ％含有し、細孔容積が０．０１～０．５ｃｍ３／ｇであって平均細孔径が３００Å以下であり、平均圧壊強度が３ｋｇ以上であることを特徴とする多孔質成形体。
  2. 　ＢＥＴ比表面積が１０～１００ｍ２／ｇである請求項１記載の多孔質成形体。
  3. 　少なくともマグネシウム及びアルミニウムを含有したハイドロタルサイトを成形し、５００℃～１５００℃の範囲で焼成して形成される請求項１記載の多孔質成形体。
  4. 　請求項１～３のいずれかに記載の多孔質成形体を用いた触媒用担体。
  5. 　請求項１～３のいずれかに記載の多孔質成形体を用いた触媒。
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US9388082B2 (en) 2016-07-12
JP5168498B2 (ja) 2013-03-21
EP2226308A4 (en) 2011-11-30
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