WO2010084645A1 - Catalyseur acide solide ayant une structure de nanotube - Google Patents

Catalyseur acide solide ayant une structure de nanotube Download PDF

Info

Publication number
WO2010084645A1
WO2010084645A1 PCT/JP2009/066478 JP2009066478W WO2010084645A1 WO 2010084645 A1 WO2010084645 A1 WO 2010084645A1 JP 2009066478 W JP2009066478 W JP 2009066478W WO 2010084645 A1 WO2010084645 A1 WO 2010084645A1
Authority
WO
WIPO (PCT)
Prior art keywords
acid catalyst
solid acid
reaction
metal
titanium oxide
Prior art date
Application number
PCT/JP2009/066478
Other languages
English (en)
Japanese (ja)
Inventor
政明 北野
亨和 原
Original Assignee
財団法人神奈川科学技術アカデミー
国立大学法人東京工業大学
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 財団法人神奈川科学技術アカデミー, 国立大学法人東京工業大学 filed Critical 財団法人神奈川科学技術アカデミー
Priority to JP2010547397A priority Critical patent/JPWO2010084645A1/ja
Publication of WO2010084645A1 publication Critical patent/WO2010084645A1/fr

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
    • 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
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; 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
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/066—Zirconium or hafnium; 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
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/20—Vanadium, niobium or tantalum
    • 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
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J35/23—
    • B01J35/30—
    • B01J35/58—
    • B01J35/615—
    • B01J35/647—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • C01G23/047—Titanium dioxide
    • 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
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/62227—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres
    • C04B35/62231—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres based on oxide ceramics
    • 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
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/62227—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres
    • C04B35/62231—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres based on oxide ceramics
    • C04B35/62236—Fibres based on aluminium oxide
    • 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
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/62227—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres
    • C04B35/62231—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres based on oxide ceramics
    • C04B35/6224—Fibres based on silica
    • 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
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/62227—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres
    • C04B35/62231—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres based on oxide ceramics
    • C04B35/6225—Fibres based on zirconium oxide, e.g. zirconates such as PZT
    • 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
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/62227—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres
    • C04B35/62231—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres based on oxide ceramics
    • C04B35/62259—Fibres based on titanium oxide
    • 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
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632—Organic additives
    • C04B35/6325—Organic additives based on organo-metallic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
    • C07C2/861—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only halogen as hetero-atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
    • C07C49/782—Ketones containing a keto group bound to a six-membered aromatic ring polycyclic
    • C07C49/784—Ketones containing a keto group bound to a six-membered aromatic ring polycyclic with all keto groups bound to a non-condensed ring
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
    • C01P2004/13—Nanotubes
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3232—Titanium oxides or titanates, e.g. rutile or anatase
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
    • C04B2235/444—Halide containing anions, e.g. bromide, iodate, chlorite
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
    • C04B2235/448—Sulphates or sulphites
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/52—Constituents or additives characterised by their shapes
    • C04B2235/5208—Fibers
    • C04B2235/526—Fibers characterised by the length of the fibers
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/52—Constituents or additives characterised by their shapes
    • C04B2235/5208—Fibers
    • C04B2235/5264—Fibers characterised by the diameter of the fibers
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/52—Constituents or additives characterised by their shapes
    • C04B2235/5284—Hollow fibers, e.g. nanotubes
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/52—Constituents or additives characterised by their shapes
    • C04B2235/5296—Constituents or additives characterised by their shapes with a defined aspect ratio, e.g. indicating sphericity
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5409—Particle size related information expressed by specific surface values
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof

Definitions

  • the present invention relates to a novel solid acid catalyst.
  • solid acid catalysts such as silicates, zeolites and various metal oxides have been widely used in various fields such as alkylation reaction of organic compounds and hydrolysis of carbohydrates. Since solid acid catalysts are solid, they have advantages of being more convenient to handle than liquid acid catalysts such as sulfuric acid and being easy to separate from products after use. Yes.
  • fibrous titanium oxide can be obtained by hydrothermally treating titanium oxide powder with a concentrated aqueous alkali solution.
  • Photocatalysts, dye-sensitized solar cells, sensors, catalyst carriers, ion exchange materials Numerous studies have been conducted for the purpose of application. However, there is no example applied as a solid acid catalyst.
  • an object of the present invention is to provide a novel solid acid catalyst having higher catalytic activity than known solid acid catalysts.
  • the present invention relates to a solid acid catalyst comprising a tubular substance obtained by heat-treating at least one selected from the group consisting of metal oxides, chlorides, sulfates and metal organic compounds in concentrated alkaline aqueous solution.
  • a solid acid catalyst comprising a tubular substance obtained by heat-treating at least one selected from the group consisting of metal oxides, chlorides, sulfates and metal organic compounds in concentrated alkaline aqueous solution.
  • the present invention also provides a solid acid catalyst of a tube-like substance obtained by heat-treating at least one selected from the group consisting of metal oxides, chlorides, sulfates and metal organic compounds in concentrated alkaline aqueous solution. Provide use for the manufacture of.
  • the present invention is a method for carrying out a chemical reaction by an acid catalyst, wherein the acid catalyst comprises at least one selected from the group consisting of metal oxides, chlorides, sulfates and metal organic compounds as a concentrated alkali.
  • the acid catalyst comprises at least one selected from the group consisting of metal oxides, chlorides, sulfates and metal organic compounds as a concentrated alkali.
  • a method for carrying out a chemical reaction which is a tube-shaped substance obtained by heat treatment in an aqueous solution.
  • the solid acid catalyst of the present invention has a high acid catalyst activity, and the alkylation reaction at room temperature where the reaction hardly proceeded with various known solid acid catalysts.
  • the solid acid catalyst of the present invention was often used as a catalyst.
  • FIG. 2 is a graph showing nitrogen adsorption / desorption isotherms and pore distribution curves of the solid acid catalysts obtained in Examples 1 to 4 of the present invention.
  • FIG. The figure which shows the nitrogen adsorption / desorption isotherm and pore distribution curve of the solid acid catalyst obtained in Comparative Examples 2 and 3.
  • FIG. The figure which shows the relationship between the reaction time when the benzylation reaction of toluene was performed at room temperature using the solid acid catalyst obtained in the Example of this invention, or various well-known solid acid catalysts, and the production amount of benzyltoluene. It is.
  • FIG. 1 The FT-IR spectrum of the titanium oxide (starting material) which adsorb
  • Titanium oxide having adsorbed trimethyl phosphine oxide (TMPO) as a probe molecule shows a 31 P MAS NMR spectrum of titanium oxide nanotubes prepared in (starting material) and Example 1.
  • the solid acid catalyst of the present invention is at least one selected from the group consisting of metal oxides, chlorides, sulfates and metal organic compounds (hereinafter referred to as “metal oxides” for convenience). Is obtained by heat-treating in a concentrated alkaline aqueous solution.
  • the “metal” is preferably at least one selected from the group consisting of titanium, niobium, tungsten, zirconium, zinc, molybdenum, silicon, aluminum, and tantalum. These metals can be used alone or in combination of a plurality of types. Of these, titanium is most preferred.
  • the solid acid catalyst of the present invention is obtained by using at least one selected from the group consisting of metal organic compounds such as metal oxides, chlorides, sulfates and alkoxides (preferably having 4 to 28 carbon atoms) as a starting material. It is done. Metal organic compounds such as oxides, chlorides, sulfates, and alkoxides can be used alone or in combination. Of the metal organic compounds such as oxides, chlorides, sulfates and alkoxides, oxides are most preferable.
  • an inorganic strong base such as an alkali metal hydroxide, an inorganic weak base such as ammonia, or the like can be used.
  • an inorganic strong base such as an alkali metal hydroxide, an inorganic weak base such as ammonia, or the like.
  • alkali metal hydroxides such as NaOH and KOH are most preferred.
  • “Concentrated alkaline aqueous solution” means that the pH is 12 or more, preferably pH 13 or more, particularly 14 or more.
  • the concentration is usually about 5M to 20M, preferably about 7M to 15M.
  • the temperature during the heat treatment is preferably about 120 ° C to 180 ° C, more preferably about 140 ° C to 160 ° C.
  • the heat treatment temperature is about 200 ° C. or higher, the metal oxide or the like becomes fibrous, but it does not become a tube (that is, a solid fibrous shape without forming a hollow portion extending in the longitudinal direction of the fibrous material). May become a substance).
  • heat treatment can be performed under pressure in an autoclave or the like. If the heat treatment time is too short, the metal oxide or the like will not be in the form of a fiber (thus, naturally, it will not be in a tube shape). On the other hand, there is no advantage of making it longer than necessary and energy is wasted.
  • the amount of metal oxide used in the heat treatment step is preferably about 5% to 10%, more preferably about 6% to 8%, based on the weight of the concentrated alkaline aqueous solution. If the amount of metal oxide used is too small, it will be fibrous, but it may not be tubular. On the other hand, if the amount of metal oxide used is too large, the concentrated alkaline aqueous solution is insufficient and the metal oxide does not become fibrous.
  • the heat treatment temperature and the amount of the metal oxide or the like used in a concentrated alkaline aqueous solution are important.
  • An oxide or the like can be formed into a tube shape.
  • the heat treatment conditions can be optimized by routine experiments using these as parameters.
  • a specific surface area and a total pore volume increase rather than a specific surface area and a total pore volume of the starting raw material before heat processing.
  • the specific surface area and total pore volume of the tube-shaped substance increase by 10% or more with respect to the specific surface area and total pore volume of the starting material before heat treatment in the concentrated alkaline aqueous solution, respectively. It is preferable.
  • the specific surface area is preferably increased by 20% to 50% of the specific surface area of the starting material, and the total pore volume is preferably increased by 15% to 20% of the starting material.
  • the specific surface area and the total pore volume can be measured by a nitrogen gas adsorption / desorption method (constant volume method), which is a conventional method, and can be easily measured by a commercially available automatic measuring device using this method (see below). See example).
  • the fact that the metal oxide or the like has become a tube can be confirmed by increasing the specific surface area and the total pore volume and whether the tube shape can be observed with a transmission electron microscope (see the following examples).
  • the metal oxide or the like after the heat treatment As a solid acid catalyst, it is preferable to remove alkali metal ions by washing with water. Furthermore, after that, it is preferable to perform an acid treatment and proton exchange alkali metal ions contained in the metal oxide or the like after the heat treatment.
  • the metal oxide after the heat treatment contains a large amount of sodium ions, but it is preferable to proton-exchange sodium ions by acid treatment.
  • the acid for the acid treatment is not particularly limited, but nitric acid, sulfuric acid, hydrochloric acid and the like can be preferably used.
  • the acid concentration is preferably such that the pH is 3 or less, more preferably 1.5 or less.
  • the drying may be air drying at room temperature, or may be heat drying in a drying furnace.
  • the temperature in the case of heat drying is 200 ° C. or lower, preferably 120 ° C. or lower.
  • the metal oxide and the like are formed into a tube by the heat treatment.
  • the tube shape is a shape in which the appearance is fibrous and a hollow portion extending in the longitudinal direction is present inside the fiber. Whether it is fibrous or not can be easily determined by observing with a scanning electron microscope (see FIGS. 1A and 1B, which are scanning electron micrographs of the catalyst prepared in the following Examples).
  • FIGS. 1A and 1B which are scanning electron micrographs of the catalyst prepared in the following Examples).
  • FIG. 1C A transmission electron micrograph of the catalyst produced in the following example is shown in FIG. 1C. As shown in FIG. 1C, it can be seen from the transmission electron microscope observation that the fibrous substance is in the form of a tube.
  • the tubular material constituting the solid acid catalyst of the present invention as shown in FIG. 1C has a diameter of usually 5 nm to 20 nm, preferably 7 nm to 10 nm, a length of 100 nm to 3000 nm, preferably 500 nm to 1000 nm,
  • the diameter of the hollow portion is usually 1 nm to 15 nm, preferably 2 nm to 10 nm, and the length / diameter (aspect ratio) is usually about 5 to 600, preferably about 50 to 150.
  • the tube Since the diameter of the tube is nano-order (less than 1 ⁇ m), the tube may be referred to as “nanotube” in the following.
  • nanotube what is fibrous but does not have a hollow portion inside and is solid is sometimes referred to as “nanowire”.
  • the fibrous substance obtained by the above method has activity as an acid catalyst and can be used as it is as a solid acid catalyst.
  • the solid acid catalyst of the present invention can catalyze the same reaction as a known solid acid catalyst.
  • an alkylation reaction of an organic compound including a reaction of adding an alkyl group-containing group
  • a carbohydrate decomposition reaction It can be used for hydrolysis reaction, reaction for synthesizing 5-hydroxymethylfurfural (HMF), reaction for synthesizing biodiesel fuel from vegetable oil and alcohol.
  • the conditions for each reaction may be the same as in the prior art, but the solid acid catalyst of the present invention has a particularly high acid catalyst activity, so the reaction time is shortened or the reaction temperature is lowered as compared with the conventional solid acid catalyst. (See the examples below). Therefore, the reaction conditions when the solid acid catalyst of the present invention is used are desirably determined under industrial conditions that are industrially advantageous through routine experiments for each reaction.
  • the solid acid catalyst of the present invention is present in an amount of about 0.05% to 1%, preferably about 0.1% to 0.5%, based on the weight of the reaction mixture.
  • An alkyl group-containing group can be added to an aromatic compound by reacting at a boiling point of the aromatic compound for about 2 to 10 hours. In the solid acid catalyst of the present invention, the reaction proceeds sufficiently even at room temperature.
  • an alkyl group such as alkene, acetic anhydride, benzoyl chloride, phosgene, or an acyl group-containing group is added to an organic compound such as benzene, anisole, and phenol in addition to toluene. be able to.
  • the decomposition reaction for synthesizing HMF or the like from a saccharide such as glucose for example, water is usually added about 5 to 20 times based on the weight of the saccharide, and the solid acid catalyst of the present invention is added to the saccharide. In general, it is present in an amount of about 0.2 to 5 times, preferably about 0.5 to 2 times, and is usually reacted at a temperature of the boiling point of water to about 130 ° C. for about 2 to 6 hours.
  • a decomposition reaction can be performed.
  • levoglucosan, fructose, formic acid, levulinic acid and the like can be synthesized in addition to HMF from saccharides such as fructose, xylose, mannose, sucrose, cellobiose and maltose.
  • a polysaccharide such as cellulose
  • water is usually added about 1 to 10 times based on the weight of the polysaccharide, and the solid acid catalyst of the present invention is added to the saccharide.
  • the solid acid catalyst of the present invention is added to the saccharide.
  • it is present in an amount of 1 to 5 times, preferably 2 to 3 times, and it is usually decomposed by reacting for about 1 to 24 hours at a temperature of the boiling point of water to about 200 ° C. It can be performed.
  • polysaccharides such as starch can be hydrolyzed in addition to cellulose to produce glucose, fructose, xylose, etc., which are monosaccharides of the constituent units.
  • ethanol is usually about 0.3 to 3 times based on the weight of triglyceride.
  • the solid acid catalyst of the present invention is usually present in an amount of about 1 to 70 times, preferably about 5 to 50 times with respect to the saccharide, and at a temperature of about 50 ° C. to 130 ° C. for 2 hours to Biodiesel fuel can be synthesized by reacting for about 48 hours.
  • a biodiesel fuel such as methyl oleate in addition to ethyl oleate can be synthesized from a vegetable oil such as triglyceride and an alcohol such as methanol in addition to ethanol.
  • ⁇ -tocopherol (vitamin E) in the reaction of synthesizing ⁇ -tocopherol (vitamin E) from trimethylhydroquinone and isophytol, for example, isophytol is usually added about 0.5 to 3 times based on weight with respect to trimethylhydroquinone.
  • the solid acid catalyst is usually present in an amount of about 1 to 10 times, preferably about 2 to 6 times the saccharide, and reacted at a temperature of about 50 to 120 ° C. for about 2 to 48 hours.
  • ⁇ -tocopherol (vitamin E) can be synthesized.
  • ⁇ -tocopherol (vitamin E) was obtained from trimethylhydroquinone and phytol, phytyl halide, phytyl acetate, phytyl methanesulfonate, phytyl ethanesulfonate, phytyl benzenesulfonate, and phytyl toluenesulfonate in addition to isophytol. ) Can be synthesized.
  • FIG. 1A Scanning electron micrographs of the obtained solid acid catalyst are shown in FIG. 1A (Example 1) and FIG. 1B (Example 3). Although the raw material was powder, it turns out that it is fibrous. Furthermore, the transmission electron micrograph of the solid acid catalyst obtained in Example 1 is shown in FIG. 1C. As shown in FIG. 1C, it can be seen that the obtained solid acid catalyst is not only in the form of fibers but also in the form of tubes. The tubular shape is in good agreement with the pore distribution results described below.
  • Comparative Example 1 Production of Titanium Oxide-Derived Nanowire The same operation as in Example 1 was performed except that the temperature of the heat treatment under hydrothermal conditions was 200 ° C. It was observed that the titanium oxide powder produced a fibrous substance with a scanning electron microscope.
  • Example 5 Physicochemical properties of solid acid catalyst (1) X-ray diffraction analysis
  • the solid acid catalyst obtained in Example 1 was subjected to X-ray diffraction (XRD) analysis using Ultima IV manufactured by Rigaku. The results are shown in FIG.
  • XRD X-ray diffraction
  • FIG. 2 An XRD pattern of the titanium oxide powder used as a starting material is also shown.
  • TNW-1 represents the results for the solid acid catalyst of Example 1
  • TiO 2 represents the titanium oxide powder starting material.
  • the starting titanium oxide powder has a 100% anatase structure, but the titanium oxide nanowires cannot be clearly distinguished because the peaks are broad, but around 10, 24, 28, and 48 °. Peaks are observed, H 2 Ti 3 O 7 , H 2 Ti 2 O 4 (OH) 2 , H 2 Ti 4 O 9 ⁇ H 2 O, H x Ti 2-x / 4 ⁇ x / 4 O 4 ( ⁇ Means a defect), and is considered to have a structure of either H 2 O, H 2 Ti 5 O 11 or H 2 O.
  • FIG. 3 shows nitrogen adsorption / desorption isotherms and pore distribution curves of the solid acid catalysts obtained in Examples 1 to 4.
  • the nitrogen adsorption / desorption isotherm and the pore distribution curve were measured using NOVA 4200e manufactured by Quantachrome, which is a commercially available measuring apparatus using a nitrogen gas adsorption / desorption method (constant volume method) which is a conventional method.
  • the specific surface area and pore volume obtained from these measurements are summarized in Table 1 below.
  • the specific surface area of the starting titanium oxide powder is 292 m 2 / g
  • the solid acid catalyst of Example 1 in which the titanium oxide powder (5 g) was treated at 150 ° C. for 20 hours has a specific surface area of 400 m. It was found to increase to 2 / g. Even when the treatment time was increased, no significant change was observed in the specific surface area. Furthermore, it was revealed that the pore distribution curve has pores having a distribution of about 2 nm to 7 nm.
  • Comparative Examples 4 ′ to 6 ′, 8 ′, and 10 ′ ′ show the results when the same commercially available solid acid catalyst as Comparative Examples 4 to 6, 8, and 10 is used. Moreover, it shows about the result at the time of using concentrated sulfuric acid (comparative example 13).
  • the amount of HMF produced was larger than when titanium oxide as a starting material was used.
  • the amount of HMF produced was comparable to that of hydrous niobic acid, which is known to exhibit particularly excellent catalytic activity for this reaction.
  • FIG. 8 shows FT-IR spectra of titanium oxide (starting material) and titanium oxide nanotubes produced in Example 1 on which pyridine was adsorbed as a probe molecule.
  • the peak observed near 1440 cm ⁇ 1 is absorption by pyridine coordinated to the Lewis acid point (Ti 4+ site), and this peak was observed for both titanium oxide and titanium oxide nanotubes.
  • the peak observed near 1540 cm ⁇ 1 is absorption derived from the pyridinium ion formed on the Bronsted acid point, and was observed only for the titanium oxide nanotube.
  • the titanium oxide nanotube had both a Bronsted acid point and a Lewis acid point, and the respective concentrations were 0.08 mmol / g and 0.23 mmol / g.
  • the Friedel-Crafts alkylation reaction is known to proceed efficiently with a Lewis acid, and the Lewis acid point of the titanium oxide nanotube is considered to be an active species for this reaction.
  • the turnover number at this time exceeds 350 in 3 hours. This indicates that this reaction is proceeding catalytically.
  • the reaction hardly progressed with titanium dioxide having only a Lewis acid point, it is considered that the Bronsted acid point of the titanium oxide nanotube also contributes to the activity improvement.
  • the above FT-IR spectroscopic analysis was performed using an IR cell connected to a closed circulation system.
  • a 25 mg mg sample was molded into a 20 mm diameter disk, placed in a cell, and then evacuated at 150 ° C. for 1 hour. Then, after cooling to room temperature, pyridine was introduced as a probe molecule and measured at room temperature.
  • CO as a probe molecule
  • the cell was cooled to near liquid nitrogen temperature, CO was introduced, and the sample was adsorbed on the sample for measurement.
  • FIG. 10 shows 31 P MAS NMR spectra of titanium oxide (starting material) adsorbing trimethylphosphine oxide (TMPO) as a probe molecule and the titanium oxide nanotube produced in Example 1. Indicates. It is known that the acid strength increases as the 31 P peak shifts to the lower magnetic field side. That is, it was found that the strength of Bronsted acid points was higher in titanium oxide nanotubes than in titanium oxide. This acid strength was found to be comparable to that of hydrous niobic acid.
  • TMPO trimethylphosphine oxide
  • the solid acid catalyst of the present invention functions well as an acid catalyst even under room temperature conditions where the reaction hardly proceeds with known solid acid catalysts. Therefore, the solid acid catalyst of the present invention exhibits excellent performance as a solid acid catalyst such as an alkylation reaction of an organic compound and a decomposition reaction of a carbohydrate.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Nanotechnology (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Composite Materials (AREA)
  • Catalysts (AREA)
  • Furan Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention concerne un nouveau catalyseur acide solide qui a une activité catalytique plus élevée que celle des catalyseurs acides solides classiques. Le catalyseur acide solide a été mis au point en se fondant sur la découverte selon laquelle une substance d'oxyde de titane de type tube produite par addition d'une poudre d'oxyde de titane à une solution aqueuse alcaline concentrée et chauffage du mélange obtenu en conditions hydrothermiques a une excellente activité catalytique acide. Le catalyseur acide solide comprend une substance de type tube produite par traitement thermique d'au moins un composé choisi dans un ensemble consistant en un oxyde d'un métal, un chlorure d'un métal, un sulfate d'un métal et un composé organométallique dans une solution aqueuse alcaline concentrée.
PCT/JP2009/066478 2009-01-20 2009-09-24 Catalyseur acide solide ayant une structure de nanotube WO2010084645A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2010547397A JPWO2010084645A1 (ja) 2009-01-20 2009-09-24 ナノチューブ構造を有する固体酸触媒

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2009-009465 2009-01-20
JP2009009465 2009-01-20

Publications (1)

Publication Number Publication Date
WO2010084645A1 true WO2010084645A1 (fr) 2010-07-29

Family

ID=42355715

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2009/066478 WO2010084645A1 (fr) 2009-01-20 2009-09-24 Catalyseur acide solide ayant une structure de nanotube

Country Status (2)

Country Link
JP (1) JPWO2010084645A1 (fr)
WO (1) WO2010084645A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102350331A (zh) * 2011-08-22 2012-02-15 浙江工业大学 超声-水热耦合制备TiO2纳米管的方法
JP2012211031A (ja) * 2011-03-30 2012-11-01 Osaka Gas Co Ltd 高アスペクト比の金属ナノ構造体の単離方法
TWI602612B (zh) * 2016-10-24 2017-10-21 張志雄 一種高性能酸性觸媒顆粒之製備方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003137549A (ja) * 2001-10-30 2003-05-14 Catalysts & Chem Ind Co Ltd 管状酸化チタン粒子の製造方法および管状酸化チタン粒子
WO2006087841A1 (fr) * 2005-02-17 2006-08-24 Osaka University Nanotube d’oxyde de titane et procédé de fabrication idoine
JP2007130267A (ja) * 2005-11-10 2007-05-31 Catalysts & Chem Ind Co Ltd 管状酸化チタン粒子からなる消臭剤

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003137549A (ja) * 2001-10-30 2003-05-14 Catalysts & Chem Ind Co Ltd 管状酸化チタン粒子の製造方法および管状酸化チタン粒子
WO2006087841A1 (fr) * 2005-02-17 2006-08-24 Osaka University Nanotube d’oxyde de titane et procédé de fabrication idoine
JP2007130267A (ja) * 2005-11-10 2007-05-31 Catalysts & Chem Ind Co Ltd 管状酸化チタン粒子からなる消臭剤

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
BAVYKIN D V ET AL.: "The effect of hydrothermal conditions on the mesoporous structure of Ti02 nanotubes", J. MATER. CHEM., vol. 14, no. 22, 21 November 2004 (2004-11-21), pages 3370 - 3377 *
KUBO TAKASHI ET AL.: "Local Strucure of TiO2-Derived Nanotubes Prepared by Hydrothermal Process", J. PHYS. CHEM. C, vol. 112, no. 5, 7 February 2008 (2008-02-07), pages 1658 - 1662 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012211031A (ja) * 2011-03-30 2012-11-01 Osaka Gas Co Ltd 高アスペクト比の金属ナノ構造体の単離方法
CN102350331A (zh) * 2011-08-22 2012-02-15 浙江工业大学 超声-水热耦合制备TiO2纳米管的方法
TWI602612B (zh) * 2016-10-24 2017-10-21 張志雄 一種高性能酸性觸媒顆粒之製備方法

Also Published As

Publication number Publication date
JPWO2010084645A1 (ja) 2012-07-12

Similar Documents

Publication Publication Date Title
Wu et al. Selectivity control in photocatalytic valorization of biomass-derived platform compounds by surface engineering of titanium oxide
Kang et al. Depolymerization of PET into terephthalic acid in neutral media catalyzed by the ZSM-5 acidic catalyst
Peng et al. Hydrothermally stable Nb-SBA-15 catalysts applied in carbohydrate conversion to 5-hydroxymethyl furfural
Wang et al. Glucose production from hydrolysis of cellulose over a novel silica catalyst under hydrothermal conditions
Zhou et al. Sulfonated hierarchical H-USY zeolite for efficient hydrolysis of hemicellulose/cellulose
Liu et al. Efficient biomass transformations catalyzed by graphene-like nanoporous carbons functionalized with strong acid ionic liquids and sulfonic groups
Wang et al. Ultrafine single-crystal TiOF 2 nanocubes with mesoporous structure, high activity and durability in visible light driven photocatalysis
RU2528389C2 (ru) Вольфрамкарбидные катализаторы на мезопористом углеродном носителе, их получение и применения
Liu et al. Glucose conversion to methyl levulinate catalyzed by metal ion-exchanged montmorillonites
Wang et al. Sn-doped Pt catalyst supported on hierarchical porous ZSM-5 for the liquid-phase hydrogenation of cinnamaldehyde
Cao et al. Visible-light-driven prompt and quantitative production of lactic acid from biomass sugars over a N-TiO 2 photothermal catalyst
Liu et al. Highly efficient conversion of glucose into methyl levulinate catalyzed by tin-exchanged montmorillonite
Mu et al. Microwave-assisted synthesis of highly dispersed ZrO2 on CNTs as an efficient catalyst for producing 5-hydroxymethylfurfural (5-HMF)
Chagas et al. Metal-free bifunctional silica for conversion of waste glycerol from biodiesel: sustainable production of formic acid
Wang et al. Enhancing tungsten oxide/SBA-15 catalysts for hydrolysis of cellobiose through doping ZrO2
Kumar et al. Preparation and catalytic activity of thermosensitive Ga2O3 nanorods
Akti et al. Role of synthesis media on properties of tin and copper incorporated SBA-15 catalysts and their activity in selective oxidation of ethanol
WO2010084645A1 (fr) Catalyseur acide solide ayant une structure de nanotube
Lu et al. Effective isomerization of glucose to fructose by Sn-MFI/MCM-41 composites as Lewis acid catalysts
He et al. Synthesis of titanium containing MCM-41 and its application for catalytic hydrolysis of cellulose
Yousatit et al. Selective synthesis of 5-hydroxymethylfurfural over natural rubber–derived carbon/silica nanocomposites with acid–base bifunctionality
Murillo et al. Conversion of sugars to methyl lactate with exfoliated layered stannosilicate UZAR-S4
Mayani et al. Development of nanocarbon gold composite for heterogeneous catalytic oxidation
KR100995982B1 (ko) 경질 주형안에서 제조된 메조 기공 실리카 나노 섬유를 이용한 촉매로의 응용 및 이의 촉매 활성도 조절
Ye et al. Plasmon resonance enhanced palygorskite-based composite toward the photocatalytic reformation of cellulose biomass under full spectrum

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 09838835

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2010547397

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 09838835

Country of ref document: EP

Kind code of ref document: A1