WO2015079955A1 - 固体塩基触媒並びにこれに関する方法及び反応装置 - Google Patents

固体塩基触媒並びにこれに関する方法及び反応装置 Download PDF

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WO2015079955A1
WO2015079955A1 PCT/JP2014/080400 JP2014080400W WO2015079955A1 WO 2015079955 A1 WO2015079955 A1 WO 2015079955A1 JP 2014080400 W JP2014080400 W JP 2014080400W WO 2015079955 A1 WO2015079955 A1 WO 2015079955A1
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Prior art keywords
solid base
base catalyst
atom
boron
raw material
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English (en)
French (fr)
Japanese (ja)
Inventor
靖雄 今城
純一 尾崎
尚克 神成
康傑 松永
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Nisshinbo Holdings Inc
Gunma University NUC
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Nisshinbo Holdings Inc
Gunma University NUC
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
    • 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
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties

Definitions

  • the present invention relates to a solid base catalyst and a method and a reaction apparatus related to the solid base catalyst, and more particularly to improvement of the activity of the solid base catalyst.
  • Examples of solid base catalysts used in base-catalyzed reactions such as carbon-carbon bond forming reactions include magnesium oxide that exhibits activity in various base-catalyzed reactions (see, for example, Patent Document 1).
  • Patent Document 2 and Non-Patent Document 1 describe using a carbon material doped with nitrogen as a solid base catalyst in a chemical reaction.
  • magnesium oxide has a problem that it is unstable in the air because it reacts with moisture and carbon dioxide in the air. Moreover, the catalytic activity (for example, the yield of the reaction product) of the conventional carbon material described in Patent Document 2 and Non-Patent Document 1 is not always sufficient as compared with that of magnesium oxide.
  • the present invention has been made in view of the above problems, and an object thereof is to provide a solid base catalyst having improved activity, a method and a reaction apparatus related thereto.
  • a solid base catalyst according to an embodiment of the present invention for solving the above-described problems includes a carbonized material containing nitrogen atoms and boron atoms. According to the present invention, a solid base catalyst having improved activity can be provided.
  • the boron atom / carbon atom ratio measured by X-ray photoelectron spectroscopy of the carbonized material may be 0.04 to 0.35.
  • the carbonized material may have a nitrogen atom / carbon atom ratio measured by X-ray photoelectron spectroscopy of 0.08 to 0.30.
  • the carbonized material may have a (boron atom + nitrogen atom) / carbon atom ratio measured by X-ray photoelectron spectroscopy of 0.12 to 0.65.
  • the carbonized material may further contain oxygen atoms. In this case, the oxygen atom / carbon atom ratio measured by X-ray photoelectron spectroscopy of the carbonized material may be 0.10 to 0.50.
  • the solid base catalyst when used in a Kunefener gel reaction for obtaining ethyl cyanocinnamate by a chemical reaction between ethyl cyanoacetate and benzaldehyde, the yield of ethyl cyanocinnamate is 60% or more. Such catalytic activity may be exhibited.
  • the solid base catalyst when used in a Knefenagel reaction for obtaining ethyl cyanocinnamate by a chemical reaction between ethyl cyanoacetate and benzaldehyde, the selectivity of the ethyl cyanocinnamate is 70% or more. Such catalytic activity may be exhibited.
  • the solid base catalyst may be carbonized of a raw material containing an organic substance, and the following (a) and / or (b): (a) using the raw material containing a nitrogen atom and / or a boron atom; (B) including the carbonized material produced by a method including doping nitrogen atoms and / or boron atoms during the carbonization; and obtaining a carbonized material containing nitrogen atoms and boron atoms. It is good as well.
  • a reaction apparatus for solving the above-described problems includes any one of the solid base catalysts.
  • ADVANTAGE OF THE INVENTION According to this invention, the reaction apparatus containing the solid base catalyst with improved activity can be provided.
  • a method according to an embodiment of the present invention for solving the above-described problem is characterized in that any one of the solid base catalysts is used for a chemical reaction.
  • ADVANTAGE OF THE INVENTION According to this invention, the method of using the solid base catalyst with improved activity for a chemical reaction can be provided.
  • the method for producing a solid base catalyst according to an embodiment of the present invention for solving the above-described problems includes carbonization of a raw material containing an organic substance, and the following (a) and / or (b): (a) nitrogen Using the raw material containing atoms and / or boron atoms; (b) doping nitrogen atoms and / or boron atoms during the carbonization; and a solid comprising a carbonized material containing nitrogen atoms and boron atoms Obtaining a base catalyst.
  • ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the solid base catalyst with improved activity can be provided.
  • the manufacturing method of the said solid base catalyst includes using the said raw material containing a nitrogen atom as said (a), and dope a boron atom during the said carbonization as said (b), It is good also as including. Moreover, the manufacturing method of the said solid base catalyst is good also as doping the boron atom using the boron atom containing gas during the said carbonization as said (b). Moreover, the manufacturing method of the said solid base catalyst is good also as using the said raw material containing a nitrogen atom and a boron atom as said (a).
  • a solid base catalyst according to an embodiment of the present invention for solving the above-described problems is characterized by being produced by any one of the methods described above. According to the present invention, a solid base catalyst having improved activity can be provided.
  • the solid base catalyst (this catalyst) is a solid base catalyst containing a carbonized material containing nitrogen atoms and boron atoms. That is, this catalyst is a heterogeneous catalyst that contains a carbonized material having a carbon structure containing nitrogen and boron atoms and exhibits catalytic activity in a basic chemical reaction.
  • the carbonization material contained in this catalyst is obtained by carbonizing the raw material containing organic substance as mentioned later.
  • the boron atom / carbon atom ratio (B / C ratio) measured by X-ray photoelectron spectroscopy of the carbonized material of the present catalyst may be, for example, 0.04 to 0.35.
  • the B / C ratio of the carbonized material is the ratio of the boron atom content (%) to the carbon atom content (%) measured in the X-ray photoelectron spectroscopy of the carbonized material. It is preferable that the B / C ratio of the carbonized material of the present catalyst is within this range in view of excellent catalytic activity of the present catalyst.
  • the B / C ratio of the carbonized material of the present catalyst is preferably 0.06 to 0.35, for example. That is, it is particularly preferable that the B / C ratio of the carbonized material of the present catalyst is within this range in view of excellent catalytic activity of the present catalyst.
  • the nitrogen atom / carbon atom ratio (N / C ratio) measured by X-ray photoelectron spectroscopy of the carbonized material of the present catalyst may be, for example, 0.08 to 0.30. It is preferable that the N / C ratio of the carbonized material of the present catalyst is within this range in view of excellent catalytic activity of the present catalyst.
  • the (boron atom + nitrogen atom) / carbon atom ratio ((B + N) / C ratio) measured by X-ray photoelectron spectroscopy of the carbonized material of the present catalyst is, for example, 0.12 to 0.65. It is good as well.
  • the (B + N) / C ratio of the carbonized material is such that the boron atom content (%) and nitrogen atom content relative to the carbon atom content (%) measured in the X-ray photoelectron spectroscopy of the carbonized material. It is a ratio of the total with content rate (%). It is preferable that the (B + N) / C ratio of the carbonized material of the present catalyst is within this range in view of the excellent catalytic activity of the present catalyst.
  • the (B + N) / C ratio of the carbonized material of the present catalyst is, for example, preferably 0.16 to 0.65, more preferably 0.17 to 0.65, and 0.18 to Particularly preferred is 0.65. That is, it is particularly preferable that the (B + N) / C ratio of the carbonized material of the present catalyst is within these ranges in view of the excellent catalytic activity of the present catalyst.
  • the carbonized material contained in the present catalyst may further contain oxygen atoms. That is, in this case, the catalyst includes a carbonized material having a carbon structure including a nitrogen atom, a boron atom, and an oxygen atom.
  • the oxygen atom / carbon atom ratio (O / C ratio) measured by X-ray photoelectron spectroscopy of the carbonized material is 0.10 to 0.50. It is good as well. It is preferable that the O / C ratio of the carbonized material of the present catalyst is within this range in view of excellent catalytic activity of the present catalyst.
  • the O / C ratio of the carbonized material of the present catalyst is, for example, preferably 0.16 to 0.50, more preferably 0.17 to 0.50, and 0.18 to 0.00. 50 is particularly preferred. That is, it is particularly preferable that the O / C ratio of the carbonized material of the present catalyst is within these ranges from the viewpoint of excellent catalytic activity of the present catalyst.
  • the B / C ratio, N / C ratio, (B + N) / C ratio, and O / C ratio of the carbonized material of the present catalyst may be any combination within the above-described range. That is, for example, the carbonized material of the present catalyst may have a B / C ratio of 0.04 to 0.35 and a (B + N) / C ratio of 0.12 to 0.65, for example.
  • the carbonization material of the present catalyst preferably has a B / C ratio of 0.06 to 0.35 and a (B + N) / C ratio of 0.12 to 0.65.
  • the (B + N) / C ratio of the carbonized material of the catalyst is preferably 0.16 to 0.65, more preferably 0.17 to 0.65, and 0.18. Particularly preferred is .about.0.65.
  • the carbonized material of the present catalyst preferably has, for example, a B / C ratio of 0.04 to 0.35 and a (B + N) / C ratio of 0.16 to 0.65, preferably 0.17 Is more preferably from 0.65 to 0.65, particularly preferably from 0.18 to 0.65. Furthermore, in this case, the B / C ratio of the carbonized material of the present catalyst is preferably 0.06 to 0.35.
  • the O / C ratio of the carbonized material of the present catalyst may be 0.10 to 0.50 in any of the combinations of the B / C ratio and the (B + N) / C ratio described above.
  • the O / C ratio of the carbonized material of the present catalyst is preferably, for example, 0.16 to 0.50, more preferably 0.17 to 0.50, and 0.18 to 0. Particularly preferred is .50.
  • the N / C ratio of the carbonized material of the catalyst may be 0.08 to 0.30.
  • the carbonized material of the present catalyst may not contain a metal (for example, a transition metal) inside. That is, in this case, the present catalyst contains a carbonized material containing nitrogen atoms and boron atoms, and containing no metal (for example, transition metal) inside. In addition, the present catalyst includes a carbonized material containing an organic substance and containing a nitrogen atom and a boron atom obtained by carbonization of a raw material not containing a metal (for example, a transition metal) and not containing the metal inside. It is good as well.
  • a metal for example, a transition metal
  • the carbonized material of the present catalyst may not include a metal (for example, a transition metal) on the surface.
  • the carbonization material of this catalyst is good also as not including a noble metal (for example, platinum) on the surface.
  • the carbonization material of this catalyst is good also as not including a metal (for example, transition metal) in the surface and an inside.
  • This catalyst is used as a solid base catalyst in chemical reactions. That is, one of the methods according to this embodiment is a method of using the above-described solid base catalyst (the present catalyst) for a chemical reaction. In this method, for example, a reaction product and the present catalyst are brought into contact with each other in a solution to obtain a reaction product generated by a chemical reaction of the reactant.
  • This catalyst is used, for example, for base catalyzed reactions (chemical reactions catalyzed by bases).
  • the base catalyzed reaction may be, for example, a carbon-carbon bond forming reaction and / or a transesterification reaction.
  • the carbon-carbon bond forming reaction is an important chemical reaction for forming a molecular skeleton in fine chemistry for synthesizing drugs and basic chemicals, for example.
  • the transesterification reaction is an important chemical reaction used to synthesize biodiesel fuel, for example.
  • the carbon-carbon bond forming reaction may be, for example, a Kunafener gel reaction (Kunafener gel condensation) or an aldol reaction (aldol condensation). And one or more selected from the group consisting of Michael reaction (Michael addition).
  • the present catalyst when used for the Knefenergel reaction, for example, by chemically reacting (dehydrating condensation) an active methylene compound and an aldehyde or a ketone in the presence of the present catalyst, A reaction product may be obtained.
  • a fatty acid such as vegetable oil and fat and a lower alcohol such as methanol are chemically reacted to produce a fatty acid. It is good also as obtaining reaction products, such as methyl ester.
  • reaction products such as methyl ester.
  • fatty acid methyl ester can be used as a biodiesel fuel.
  • the present catalyst exhibits an excellent basic catalytic activity, the product can be obtained in a high yield by using the present catalyst for the chemical reaction as described above. That is, for example, when this catalyst is used in a Knefenagel reaction to obtain ethyl cyanocinnamate by a chemical reaction between ethyl cyanoacetate and benzaldehyde, the yield of the ethyl cyanocinnamate is 60% or more. Such catalytic activity may be exhibited.
  • the present catalyst preferably exhibits catalytic activity such that the yield of ethyl cyanocinnamate is 70% or more, and more preferably exhibits catalytic activity such that the yield is 75% or more.
  • the yield (%) of ethyl cyanocinnamate was calculated as a percentage of the amount of ethyl cyanocinnamate actually obtained relative to the amount of ethyl cyanocinnamate that could be theoretically obtained.
  • the selectivity of the ethyl cyanocinnamate becomes 70% or more.
  • the catalyst preferably exhibits a catalytic activity such that the selectivity for ethyl cyanocinnamate is 75% or more.
  • the selectivity (%) of ethyl cyanocinnamate indicates the reaction selectivity (the ratio at which the target product is obtained), and the ratio of the amount of ethyl cyanocinnamate to the amount of benzaldehyde consumed is expressed as a percentage. Calculated.
  • this catalyst when this catalyst is used in a Knephenagel reaction for obtaining ethyl cyanocinnamate by a chemical reaction between ethyl cyanoacetate and benzaldehyde, for example, the yield of the ethyl cyanocinnamate is 60% or more.
  • the catalyst activity may be such that the selectivity of the ethyl cyanocinnamate is 70% or more.
  • the present catalyst preferably exhibits catalytic activity such that the yield of ethyl cyanocinnamate is 70% or more, and more preferably exhibits catalytic activity such that the yield is 75% or more. In these cases, the catalyst preferably exhibits a catalytic activity such that the selectivity for ethyl cyanocinnamate is 75% or more.
  • the reaction apparatus includes the above-described solid base catalyst (this catalyst).
  • This apparatus is preferably used in a method in which the above-described catalyst is used for a chemical reaction.
  • the apparatus includes, for example, a base material on which the present catalyst is supported, and a housing portion that includes the base material so that the present catalyst and the reactant can be brought into contact with each other.
  • the catalyst supported on the base material and the reactant are brought into contact with each other in the casing.
  • a chemical reaction is performed, and a reaction product generated by the chemical reaction can be obtained.
  • this production method carbonization of a raw material containing an organic substance and the following (a) and / or (b): (a) using the raw material containing a nitrogen atom and / or a boron atom; (b) Doping with nitrogen and / or boron atoms during the carbonization; and obtaining a solid base catalyst comprising a carbonized material containing nitrogen and boron atoms.
  • the organic substance contained in the raw material is not particularly limited as long as it is an organic substance that is carbonized. That is, the raw material may contain an organic compound.
  • the organic compound may be, for example, an organic polymer (synthetic polymer and / or natural polymer) or a low molecular weight organic compound.
  • the raw material may include biomass.
  • the organic substance is, for example, acrylonitrile, polyacrylonitrile, melamine, melamine resin, pyrrole, polypyrrole, 3-methylpolypyrrole, polyvinylpyrrole, thiazole, pyrazole, vinylpyridine, polyvinylpyridine, pyridazine, pyrimidine, piperazine, imidazole, 1 -Methylimidazole, 2-methylimidazole, quinoxaline, aniline, polyaniline, benzimidazole, polybenzimidazole, hydrazine, polycarbazole, triazine, polycarbodiimide, chelate resin, polyamideimide resin, polyacrylonitrile-polymethacrylic Acid copolymer, oxazole, morpholine, succinic dihydrazide, adipic dihydrazide, polybismaleimide, polyaminobismaleimide, Liimide, polyacrylamide, polyamide,
  • a raw material containing a nitrogen atom and / or a boron atom may be used. That is, in this case, the production method includes carbonization of a raw material containing an organic substance and containing a nitrogen atom and / or a boron atom. More specifically, the raw material contains, for example, an organic substance and may contain a nitrogen atom, may contain an organic substance and may contain a boron atom, may contain an organic substance, and may contain a nitrogen atom and a boron atom. Good. By carbonizing a raw material containing nitrogen atoms and / or boron atoms, a carbonized material containing nitrogen atoms and / or boron atoms can be obtained.
  • the raw material may contain, for example, a nitrogen atom-containing compound.
  • the said raw material is good also as not containing a boron atom.
  • the nitrogen atom-containing compound is not particularly limited as long as it is a compound containing a nitrogen atom in the molecule.
  • the nitrogen atom-containing compound is, for example, acrylonitrile, polyacrylonitrile, melamine, melamine resin, pyrrole, polypyrrole, 3-methylpolypyrrole, polyvinylpyrrole, thiazole, pyrazole, vinylpyridine, polyvinylpyridine, pyridazine, pyrimidine, piperazine, Imidazole, 1-methylimidazole, 2-methylimidazole, quinoxaline, aniline, polyaniline, benzimidazole, polybenzoimidazole, hydrazine, polycarbazole, triazine, polycarbodiimide, chelate resin, polyamideimide resin, polyacrylonitrile -Polymethacrylic acid copolymer, oxazole, morpholine, succinic dihydrazide, adipic
  • the raw material may contain, for example, a boron atom-containing compound.
  • the said raw material is good also as not containing a nitrogen atom.
  • the boron atom-containing organic compound is not particularly limited as long as it is a compound containing a boron atom in its molecule.
  • the boron atom-containing compound is selected from the group consisting of boric acid, boron trifluoride methanol complex, 9-BBN (9-borabicyclo [3.3.1] nonane), boron carbide and boron oxide, for example. It is good also as being 1 or more types.
  • the said raw material is good also as including a nitrogen atom containing compound and a boron atom containing compound, for example.
  • the nitrogen atom-containing compound and the boron atom-containing compound may be, for example, any combination of the nitrogen atom-containing compound and the boron atom-containing compound described above.
  • the raw material may contain oxygen atoms. That is, in this case, the production method includes carbonizing a raw material containing an organic substance and containing an oxygen atom. More specifically, the raw material includes, for example, an organic substance, may include a nitrogen atom and an oxygen atom, may include an organic substance, may include a boron atom and an oxygen atom, includes an organic substance, includes a nitrogen atom, and a boron atom. It is good also as including an atom and an oxygen atom. By carbonizing the raw material containing oxygen atoms, a carbonized material containing oxygen atoms can be obtained.
  • the raw material may contain, for example, an oxygen atom-containing compound.
  • the oxygen atom-containing compound is not particularly limited as long as it is a compound containing an oxygen atom in its molecule.
  • the oxygen atom-containing compound is, for example, phenol resin, phenol formaldehyde resin, polyfurfuryl alcohol, furan, furan resin, epoxy resin, pyran, polysulfone, polyvinyl alcohol, polyvinyl butyral, polyester, polyether, polylactic acid.
  • Polyether-terketone cellulose, carboxymethylcellulose, lignin, polyacrylic acid, polyacrylic ester, polymethacrylic ester, polymethacrylic acid, chelate resin, polyamideimide resin, polyacrylonitrile-polymethacrylic acid copolymer , Oxazole, morpholine, succinic dihydrazide, adipic dihydrazide, polybismaleimide, polyaminobismaleimide, polyimide, polyacrylamide, polyamide, key Emissions, chitosan, proteins, peptides, amino acids, polyamino acids, nucleic acids, hydrazides, urea, salen, may be at least one selected from the group consisting of polyurethane and polyamide amine.
  • the raw material may contain a compound containing a nitrogen atom and an oxygen atom in the molecule.
  • compounds containing nitrogen atoms and oxygen atoms in the molecule include, for example, polyamideimide resin, polyacrylonitrile-polymethacrylic acid copolymer, oxazole, morpholine, succinic dihydrazide, adipic dihydrazide, polybismaleimide, One or more selected from the group consisting of polyamino bismaleimide, polyimide, polyacrylamide, polyamide, chitin, chitosan, protein, peptide, amino acid, polyamino acid, nucleic acid, hydrazide, urea, salen, polyurethane, polyamidoamine and chelate resin It may be there.
  • the raw material may contain a compound containing a boron atom and an oxygen atom in the molecule.
  • a compound containing a boron atom and an oxygen atom in the molecule includes, for example, boric acid, boron trifluoride methanol complex, 9-BBN (9-borabicyclo [3.3.1] nonane), boron carbide and It may be one or more selected from the group consisting of boron oxide.
  • the raw material may not contain a metal (for example, a transition metal). That is, in this case, the present production method includes carbonization of a raw material containing an organic substance and not containing a metal (for example, a transition metal). By carbonizing a raw material that does not contain a metal (for example, a transition metal), a carbonized material that does not contain the metal is obtained.
  • a metal for example, a transition metal
  • the carbonization of the raw material is performed by heating the raw material to raise the temperature to a predetermined temperature (carbonization temperature) and holding the raw material at the carbonization temperature.
  • the carbonization temperature is not particularly limited as long as the organic substance contained in the raw material is carbonized.
  • the carbonization temperature may be 300 ° C. or higher, may be 400 ° C. or higher, and is 500 ° C. or higher. It is good as well.
  • the upper limit value of the carbonization temperature is not particularly limited, but the carbonization temperature may be, for example, 1500 ° C. or less.
  • the heating rate when heating the raw material to the carbonization temperature is not particularly limited, and may be, for example, 0.5 ° C./min or more and 300 ° C./min or less.
  • the time for holding the raw material at the carbonization temperature is not particularly limited as long as the organic matter contained in the raw material is carbonized, and may be, for example, 5 minutes or longer.
  • the upper limit of the carbonization time is not particularly limited, but the carbonization time may be, for example, 900 minutes or less.
  • nitrogen atoms and / or boron atoms may be doped during carbonization. That is, in this case, during the carbonization of the raw material, a treatment for doping nitrogen atoms and / or a treatment for doping boron atoms is performed so that a carbonized material containing nitrogen atoms and / or boron atoms is obtained by the carbonization. .
  • the doping treatment during carbonization may be performed only while heating the raw material and raising the temperature to a predetermined carbonization temperature, or the temperature has reached the carbonization temperature. Thereafter, the doping treatment may be performed only while the raw material is held at the carbonization temperature, the raw material is heated and the temperature is increased to a predetermined carbonization temperature, and the raw material is The dope treatment may be performed while the carbonization temperature is maintained.
  • the method of doping nitrogen atoms during carbonization is not particularly limited.
  • nitrogen atoms may be doped using a nitrogen atom-containing gas during the carbonization. That is, in this case, a carbonized material doped with nitrogen atoms is obtained by bringing the raw material into contact with a nitrogen atom-containing gas during carbonization.
  • the nitrogen atom-containing gas is a gas containing a nitrogen atom-containing compound and is particularly a gas that can obtain a carbonized material doped with nitrogen atoms by contacting the raw material at a temperature during carbonization. Not limited.
  • the nitrogen atom-containing compound contained in the nitrogen atom-containing gas is a compound containing a nitrogen atom in its molecule, and the carbonized material doped with nitrogen atoms is brought into contact with the raw material at the temperature during carbonization.
  • the compound is not particularly limited as long as it can be obtained, for example, ammonia (NH 3 ), nitric oxide, nitrogen dioxide, acetonitrile, acrylonitrile, pyridine, pyrrole, pyrimidine, ethylamine, dimethylamine, trimethylamine, piperidine, piperazine, It may be one or more selected from the group consisting of aniline, N, N-diisopropylethylamine and tetramethylethylenediamine.
  • the content of the nitrogen atom-containing compound in the nitrogen atom-containing gas is not particularly limited as long as the nitrogen atom is doped, but the nitrogen atom-containing gas contains, for example, 5 to 100% by volume of the nitrogen atom-containing compound. It may be included.
  • the time for which the raw material is brought into contact with the nitrogen atom-containing gas is not particularly limited as long as the nitrogen atoms are doped, but may be, for example, 10 to 300 minutes.
  • doping a nitrogen atom during carbonization it is good also as not doping a boron atom during the said carbonization.
  • Nitrogen doping may be performed by an ammoxidation method.
  • a carbonized material doped with nitrogen atoms is obtained by contacting the raw material with an ammonia-containing gas in an atmosphere containing oxygen during carbonization.
  • the ammonia-containing gas may be, for example, a gas containing 5 to 100% by volume of ammonia (NH 3 ). Note that the contact between the raw material and the ammonia-containing gas in the oxygen-containing atmosphere is performed, for example, by bringing a gas containing ammonia and oxygen (for example, a gas containing ammonia and air) into contact with the raw material. It is good as well.
  • a gas containing ammonia and oxygen for example, a gas containing ammonia and air
  • the doping of nitrogen atoms may be performed by a CVD (Chemical Vapor Deposition) method.
  • CVD Chemical Vapor Deposition
  • a carbonized material doped with nitrogen atoms is obtained by bringing the raw material into contact with a gas containing a nitrogen atom-containing compound such as acetonitrile during carbonization.
  • the gas containing the nitrogen atom-containing compound is, for example, one type selected from the group consisting of the nitrogen atom-containing compound and an inert gas (for example, nitrogen (N 2 ) gas, helium (He) gas, and argon (Ar) gas) Or the like).
  • an inert gas for example, nitrogen (N 2 ) gas, helium (He) gas, and argon (Ar) gas
  • the method of doping boron atoms during carbonization is not particularly limited.
  • boron atoms may be doped using a boron atom-containing gas during carbonization. That is, in this case, the carbonized material doped with boron atoms is obtained by bringing the raw material into contact with the boron atom-containing gas during carbonization.
  • the boron atom-containing gas is a gas containing a boron atom-containing compound and is particularly a gas that can obtain a carbonized material doped with boron atoms by contacting the raw material at a temperature during carbonization. Not limited.
  • the boron atom-containing compound contained in the boron atom-containing gas is a compound containing a boron atom in its molecule, and the carbonized material doped with boron atoms is brought into contact with the raw material at the temperature during carbonization.
  • the compound is not particularly limited as long as it is a compound that can be obtained.
  • it is selected from the group consisting of boron trichloride (BCl 3 ), boron trifluoride (BF 3 ), diborane (B 2 H 4 ), and trimethylboron. It is good also as being 1 or more types.
  • the gas containing the boron atom-containing compound is, for example, one selected from the group consisting of the boron atom-containing compound and an inert gas (for example, nitrogen (N 2 ) gas, helium (He) gas, and argon (Ar) gas) Or the like).
  • an inert gas for example, nitrogen (N 2 ) gas, helium (He) gas, and argon (Ar) gas
  • the content of the boron-containing compound in the boron atom-containing gas is not particularly limited as long as boron atoms are doped, but the boron atom-containing gas may be, for example, 0.1 to 100 volumes of the boron atom-containing compound. % May be included.
  • the boron atom-containing gas when the boron atom-containing gas contains BCl 3 , the boron atom-containing gas may contain 0.1 to 100% by volume, or 0.5 to 5% by volume of the BCl 3. It is good.
  • the time for which the raw material is brought into contact with the boron atom-containing gas is not particularly limited as long as it is in a range in which boron atoms are doped, but may be, for example, 5 to 300 minutes.
  • doping a boron atom during carbonization it is good also as not doping a nitrogen atom during the said carbonization.
  • the method of doping nitrogen atoms and boron atoms during carbonization is not particularly limited.
  • nitrogen atoms are first doped using nitrogen atom-containing gas, and then boron atom-containing gas is used. May be used to dope boron atoms.
  • nitrogen atoms are first doped using a nitrogen atom-containing gas, and then the nitrogen atom-containing gas is converted into an inert gas (for example, nitrogen (N 2 ) gas, helium (He) and one or more selected from the group consisting of argon (Ar) gas), and further, the inert gas is replaced with a boron atom-containing gas, and then the boron atom-containing gas is used. It is also possible to dope boron atoms.
  • an inert gas for example, nitrogen (N 2 ) gas, helium (He) and one or more selected from the group consisting of argon (Ar) gas
  • the present production method may include, for example, using a raw material containing a nitrogen atom as (a) above, and doping with boron atoms during carbonization as (b) above.
  • the present manufacturing method may include, for example, doping boron atoms using a boron atom-containing gas during carbonization as (b) above.
  • this manufacturing method includes, for example, using a raw material containing nitrogen atoms as (a) above, and doping boron atoms using a boron atom-containing gas during carbonization as (b) above. It may be included.
  • a boron atom-containing gas By using a boron atom-containing gas, a carbonized material in which boron atoms are effectively doped can be obtained.
  • this manufacturing method is good also as using using the raw material containing a nitrogen atom and a boron atom as said (a), for example. That is, in this case, for example, this production method includes carbonization of a raw material containing an organic substance, and the following (a): (a) using the raw material containing a nitrogen atom and a boron atom; and a nitrogen atom And obtaining a solid base catalyst containing a carbonized material containing a boron atom.
  • the carbonization material containing a nitrogen atom and a boron atom is obtained by said (a) and (b). That is, in this production method, the carbonized material obtained by carbonization as described above exhibits catalytic activity as a solid base catalyst. Therefore, in this production method, the carbonized material obtained by carbonization as described above may be obtained as a solid base catalyst.
  • the present catalyst described above is preferably produced by the present production method. That is, for example, the present catalyst performs carbonization of a raw material containing an organic substance and uses the raw material containing the following (a) and / or (b): (a) nitrogen atom and / or boron atom; (B) including the carbonized material produced by a method including doping nitrogen atoms and / or boron atoms during the carbonization; and obtaining a carbonized material including nitrogen atoms and boron atoms. It is good as well.
  • Example 1-1 a raw material containing an organic substance and containing a nitrogen atom was prepared. That is, polyacrylonitrile is heated in an air atmosphere, the temperature is raised from room temperature to 150 ° C. in 30 minutes, further raised from 150 ° C. to 220 ° C. in 2 hours, and then held at 220 ° C. for 3 hours. Was made infusible. Next, the sample obtained by infusibilization was pulverized using a planetary ball mill at 750 rpm for 90 minutes. The crushed sample was obtained as a carbonization raw material.
  • the raw material was carbonized, and a boron atom was doped during the carbonization to obtain a carbonized material containing a nitrogen atom and a boron atom as a solid base catalyst. That is, the pulverized sample obtained as described above is heated under the flow of a BCl 3 / N 2 mixed gas (BCl 3 concentration: 1% by volume), and the temperature is increased from room temperature to 600 ° C. by 10 ° C. / The sample was raised in minutes and then the sample was held at 600 ° C. for 50 minutes.
  • BCl 3 / N 2 mixed gas BCl 3 concentration: 1% by volume
  • the flow gas was switched to N 2 gas, and the sample was held at 600 ° C. for 10 minutes under the N 2 gas flow. Then, under N 2 gas flow, naturally it lowers the temperature, to obtain a carbonized material. Furthermore, this carbonized material was pulverized using a planetary ball mill under the conditions of 750 rpm and 90 minutes to obtain a solid base catalyst made of the carbonized material.
  • Example 1-2 Instead of holding the sample at 600 ° C. under BCl 3 / N 2 mixed gas flow and N 2 gas flow during carbonization, the sample was held at 800 ° C. under BCl 3 / N 2 mixed gas flow and N 2 gas flow.
  • a solid base catalyst made of a carbonized material was obtained in the same manner as in Example 1-1 except that it was held in Step 1.
  • Example 1-3 Instead of holding the sample at 600 ° C. under BCl 3 / N 2 mixed gas flow and N 2 gas flow during carbonization, the sample was 1000 ° C. under BCl 3 / N 2 mixed gas flow and N 2 gas flow.
  • a solid base catalyst made of a carbonized material was obtained in the same manner as in Example 1-1 except that it was held in Step 1.
  • Example 2 In the same manner as in Example 1-1 described above, polyacrylonitrile was infusibilized, and a pulverized sample was obtained as a carbonization raw material. Next, the raw material was carbonized, and a boron atom was doped during the carbonization to obtain a carbonized material containing a nitrogen atom and a boron atom as a solid base catalyst.
  • the pulverized sample obtained as described above is heated under the flow of a BCl 3 / N 2 mixed gas (BCl 3 concentration: 1 vol%), and the temperature is increased from room temperature to 400 ° C. by 10 ° C. / The sample was raised in minutes and then the sample was held at 400 ° C. for 1 hour.
  • BCl 3 / N 2 mixed gas BCl 3 concentration: 1 vol%
  • the flow gas was switched to N 2 gas, and the sample was held at 1000 ° C. for 10 minutes under the N 2 gas flow. Then, under N 2 gas flow, naturally it lowers the temperature, to obtain a carbonized material. Furthermore, this carbonized material was pulverized using a planetary ball mill under the conditions of 750 rpm and 90 minutes to obtain a solid base catalyst made of the carbonized material.
  • Example 3 In the same manner as in Example 1-1 described above, polyacrylonitrile was infusibilized, and a pulverized sample was obtained as a carbonization raw material. Next, the raw material was carbonized, and a boron atom was doped during the carbonization to obtain a carbonized material containing a nitrogen atom and a boron atom as a solid base catalyst.
  • the pulverized sample obtained as described above is heated under the flow of a BCl 3 / N 2 mixed gas (BCl 3 concentration: 1% by volume), and the temperature is increased from room temperature to 1000 ° C. by 10 ° C. / Raised in minutes.
  • BCl 3 / N 2 mixed gas BCl 3 concentration: 1% by volume
  • the flow gas was switched to N 2 gas, and the sample was held at 1000 ° C. for 1 hour under the N 2 gas flow. Then, under N 2 gas flow, naturally it lowers the temperature, to obtain a carbonized material. Furthermore, this carbonized material was pulverized using a planetary ball mill under the conditions of 750 rpm and 90 minutes to obtain a solid base catalyst made of the carbonized material.
  • Example 4-1 a raw material containing an organic substance and containing nitrogen atoms and boron atoms was prepared. That is, polyacrylonitrile (PAN) was added to dimethylformamide (DMF) and ultrasonic irradiation was performed for 30 minutes to dissolve PAN.
  • PAN polyacrylonitrile
  • DMF dimethylformamide
  • boric acid was added so that the ratio (N: B) of nitrogen atoms contained in PAN to boron atoms contained in boric acid was 2: 1 (amount of boric acid: 36.9% by weight). ). Furthermore, boric acid was dissolved by irradiating the obtained mixed liquid with ultrasonic waves for 30 minutes. Using a rotary evaporator, the solvent (DMF) of the mixed solution was removed to obtain a solid. This solid was dried overnight at 100 ° C. under reduced pressure, and a dried sample was obtained as a raw material for carbonization.
  • DMF solvent
  • the raw material was carbonized to obtain a carbonized material containing nitrogen atoms and boron atoms as a solid base catalyst. That is, the sample obtained as described above is heated under a flow of N 2 gas, the temperature is increased from room temperature to 1000 ° C. at 10 ° C./min, and then the sample is heated at 1000 ° C. for 1 hour. Retained.
  • this carbonized material was pulverized using a planetary ball mill under the conditions of 750 rpm and 90 minutes to obtain a solid base catalyst made of the carbonized material.
  • Example 4-2 Boric acid was added so that the ratio (N: B) of nitrogen atoms contained in PAN to boron atoms contained in boric acid was 5: 1 (the amount of boric acid added: 18.9% by weight) Except for the above, a solid base catalyst made of a carbonized material was obtained in the same manner as in Example 4-1.
  • Example 4-3 Boric acid was added so that the ratio (N: B) of nitrogen atoms contained in PAN to boron atoms contained in boric acid was 10: 1 (the amount of boric acid added: 10.4% by weight) Except for the above, a solid base catalyst made of a carbonized material was obtained in the same manner as in Example 4-1.
  • Example 1-1 In the same manner as in Example 1-1 described above, polyacrylonitrile was infusibilized, and a pulverized sample was obtained as a raw material containing organic substances and containing nitrogen atoms. Next, the raw material was carbonized. That is, the sample obtained as described above is heated under N 2 gas flow, the temperature is increased from room temperature to 600 ° C. at 10 ° C./min, and then the sample is held at 600 ° C. for 1 hour. did.
  • this carbonized material was pulverized using a planetary ball mill under the conditions of 750 rpm and 90 minutes to obtain a pulverized carbonized material.
  • Comparative Example 1-2 A carbonized material was obtained in the same manner as Comparative Example 1-1 except that the sample was held at 800 ° C. for 1 hour instead of holding the sample at 600 ° C. for 1 hour during carbonization.
  • Comparative Example 1-3 A carbonized material was obtained in the same manner as Comparative Example 1-1 except that the sample was held at 1000 ° C. for 1 hour instead of holding the sample at 600 ° C. for 1 hour during carbonization.
  • the raw material was carbonized. That is, the sample obtained as described above is heated under N 2 gas flow, the temperature is increased from room temperature to 1000 ° C. at 10 ° C./min, and then the sample is held at 1000 ° C. for 1 hour. did.
  • this carbonized material was pulverized using a planetary ball mill under the conditions of 750 rpm and 90 minutes to obtain a pulverized carbonized material.
  • the solid base catalyst obtained as described above was analyzed by X-ray photoelectron spectroscopy (XPS). That is, the surface element of the carbonized material was analyzed with an X-ray photoelectron spectrometer (Kratos AXIS NOVA, manufactured by Shimadzu Corporation) (X-ray: AlK ⁇ ray, output: 10 mA ⁇ 15 kV). Specifically, the surface element concentrations (%) of carbon atoms, boron atoms, nitrogen atoms and oxygen atoms are determined from the area of each peak of the spectrum obtained by XPS measurement and the detection sensitivity coefficient, and the concentration of each element is calculated.
  • XPS X-ray photoelectron spectroscopy
  • the ratio of boron atoms to carbon atoms on the surface (B / C ratio), ratio of nitrogen atoms to carbon atoms (N / C ratio), ratio of boron atoms and nitrogen atoms to carbon atoms ((B + N)) / C ratio) and the ratio of oxygen atom to carbon atom (O / C ratio) were calculated.
  • the background for quantitative calculation was determined by the Shirley method.
  • the solid base catalyst obtained as described above was used for the base catalyst reaction, and the characteristics of the solid base catalyst were evaluated. That is, 100 mg of catalyst, 10 mmol of benzaldehyde, 10 mmol of ethyl cyanoacetate, and 5 mL of 1-butanol were weighed into a 20 mL volumetric flask containing a stir bar. The resulting mixture was stirred at 80 ° C. for 1 hour under reflux. After the reaction, the eggplant flask was cooled with cold water. The reaction solution and the catalyst were separated by suction filtration.
  • GC-FID flame ionization detector gas chromatography
  • FIG. 1 shows the B / C ratio, N / C ratio, (B + N) / C ratio and O / C ratio of the surface of each solid base catalyst, and the yield of ethyl cyanocinnamate (% ) And selectivity (%). Yield (%) was calculated as a percentage of the amount of ethyl cyanocinnamate actually obtained relative to the amount of ethyl cyanocinnamate that could be theoretically obtained.
  • the selectivity (%) represents the reaction selectivity (the ratio at which the target product is obtained), and was calculated as a percentage of the ratio of the amount of ethyl cyanocinnamate to the amount of benzaldehyde consumed.
  • Comparative Example 2 the use of a raw material containing nitrogen atoms and the doping treatment of nitrogen atoms were not performed positively, but nitrogen atoms were detected in the XPS measurement. The cause of this is unknown, but for example, the influence of a small amount of nitrogen used in the synthesis process of the phenol resin used as the raw material was considered.
  • the B / C ratio of the solid base catalyst according to the example is 0.055 to 0.242
  • the N / C ratio is 0.098 to 0.220
  • (B + N) / C The ratio was 0.153 to 0.462
  • the O / C ratio was 0.149 to 0.381.
  • the solid base catalyst according to the example has an excellent catalytic activity such that the yield in the Kunafenergel reaction is 62.5 to 84.9% and the selectivity is 75.5 to 85.2%. showed that.
  • the solid base catalyst according to the examples other than Example 4-3 had a yield in the Kunafenergel reaction of 75.5 to 84.9% and a selectivity of 75.5 to 85.2%.
  • the catalyst activity was extremely excellent.
  • the B / C ratios of the solid base catalysts according to the examples other than Example 4-3 are 0.070 to 0.242, the N / C ratio is 0.100 to 0.220, and (B + N ) / C ratio was 0.197 to 0.462, and O / C ratio was 0.195 to 0.381.
  • the solid base catalyst according to the example showed catalytic activity equal to or higher than that of magnesium oxide (Comparative Example 4).
  • the yield when the solid base catalyst according to the comparative examples other than the comparative example 4 is used in the Kunefener gel reaction is 1.3 to 60.0%, and the selectivity is 13.7 to 68. 9%.

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JP2009119423A (ja) * 2007-11-19 2009-06-04 Asahi Kasei Corp 活性ｂ−ｃ−ｎ材料及びその製造方法
JP2010083789A (ja) * 2008-09-30 2010-04-15 Hokkaido Univ 固体塩基触媒、その製造方法及びこれを使用する方法
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