WO2023149559A1 - Catalyseur pour réactions d'hydrogénation, son procédé de production et procédé de production d'un composé organique hydrogéné - Google Patents

Catalyseur pour réactions d'hydrogénation, son procédé de production et procédé de production d'un composé organique hydrogéné Download PDF

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WO2023149559A1
WO2023149559A1 PCT/JP2023/003674 JP2023003674W WO2023149559A1 WO 2023149559 A1 WO2023149559 A1 WO 2023149559A1 JP 2023003674 W JP2023003674 W JP 2023003674W WO 2023149559 A1 WO2023149559 A1 WO 2023149559A1
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copper
hydrogenation reaction
hydrogenated
catalyst
hydrogenation
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智照 水崎
寿彦 酒井
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NE Chemcat Corp
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NE Chemcat Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/06—Washing
    • 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
    • B01J37/16—Reducing
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
    • C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
    • C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/44—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring
    • C07C211/45—Monoamines
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
    • C07C217/78—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
    • C07C217/80—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings
    • C07C217/82—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring
    • C07C217/84—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring the oxygen atom of at least one of the etherified hydroxy groups being further bound to an acyclic carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C221/00—Preparation of compounds containing amino groups and doubly-bound oxygen atoms bound to the same carbon skeleton
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C225/00—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones
    • C07C225/22—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C255/58—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and singly-bound nitrogen atoms, not being further bound to other hetero atoms, bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
    • C07C41/20—Preparation of ethers by reactions not forming ether-oxygen bonds by hydrogenation of carbon-to-carbon double or triple bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/205—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring the aromatic ring being a non-condensed ring
    • 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
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/62—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by hydrogenation of carbon-to-carbon double or triple bonds
    • 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
    • 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
    • C07C49/80—Ketones containing a keto group bound to a six-membered aromatic ring containing halogen
    • C07C49/813—Ketones containing a keto group bound to a six-membered aromatic ring containing halogen polycyclic
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/303—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by hydrogenation of unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/612—Esters of carboxylic acids having a carboxyl group bound to an acyclic carbon atom and having a six-membered aromatic ring in the acid moiety
    • C07C69/616—Esters of carboxylic acids having a carboxyl group bound to an acyclic carbon atom and having a six-membered aromatic ring in the acid moiety polycyclic
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/72—Nitrogen atoms
    • C07D213/73—Unsubstituted amino or imino radicals

Definitions

  • the present disclosure relates to a hydrogenation reaction catalyst, a method for producing the same, and a method for producing a selectively hydrogenated product. More specifically, it relates to a hydrogenation catalyst capable of selectively hydrogenating unsaturated hydrocarbon groups and nitro groups, especially aromatic nitro groups.
  • hydrogenation reactions or hydrocracking reactions are extremely useful reactions.
  • a palladium catalyst has excellent reactivity in the hydrogenation reaction, but there is a problem that sites other than the target functional groups and unsaturated bonds are also hydrogenated during the hydrogenation reaction.
  • aromatic nitro compounds there are also compounds that have one or more functional groups that are hydrogenated or hydrogenolyzed in addition to the nitro group. Such aromatic nitro compounds may require selective hydrogenation or hydrogenolysis of only a portion of the hydrogenated or hydrogenolyzed functional groups.
  • Patent Document 1 a catalyst in which silver is supported on alumina
  • Patent Document 2 a palladium-carbon catalyst in which diphenyl sulfide is co-supported
  • Patent Document 3 a palladium-carbon catalyst in which palladium is selectively supported only on the surface layer of activated carbon
  • the non-platinum group catalysts used in Patent Document 1 generally have lower hydrogenation reactivity than platinum group catalysts, and thus have the problem of being difficult to use in industrial production.
  • the organic sulfur compound poisoned catalyst as proposed in Patent Document 2 has a problem that the catalyst life is short because the reactivity changes with time.
  • the palladium catalyst proposed in Patent Document 3 has a problem that the selectivity is still insufficient.
  • the present disclosure has been made in view of the above problems, and the organic compound to be hydrogenated, which has a plurality of functional groups and/or unsaturated bonds, is treated by a hydrogenation reaction with only some of the functional groups and/or unsaturated bonds. It is an object of the present invention to provide a hydrogenation reaction catalyst capable of selectively hydrogenating and having excellent catalyst durability.
  • the present disclosure has found that in conventional palladium carbon catalysts that have been used in hydrogenation reactions, palladium particles supported on carbon are further supported with copper. Therefore, the inventors have found that the above problems can be solved, and have completed the present disclosure. That is, the gist of the present disclosure is as follows.
  • a hydrogenation reaction catalyst comprising a carrier, palladium supported on the carrier, and copper supported on the palladium.
  • the hydrogenation reaction catalyst of the present disclosure is an organic compound to be hydrogenated having at least two functional groups and/or unsaturated bonds while maintaining at least one of the functional groups and/or unsaturated bonds. /or some of the unsaturated bonds can be selectively hydrogenated.
  • the hydrogenation reaction catalysts of the present disclosure hydrogenate nitro groups and/or unsaturated hydrocarbon groups, and hydrogenate aromatic ketones, aromatic chlorines, benzyl protecting groups, nitrile groups, and benzylic hydroxyl groups. It can be preferably used for a selective hydrogenation reaction that does not occur.
  • FIG. 1 is an electron micrograph of the hydrogenation reaction catalyst of Production Example 1 taken with a scanning transmission electron microscope.
  • FIG. 2 is a monochrome photograph in which a portion of FIG. 1 is enlarged and the metal composition is visualized.
  • a hydrogenation catalyst according to the present disclosure comprises a support, palladium supported on the support, and copper supported on the palladium.
  • the hydrogenation reaction catalyst according to the present disclosure supports copper on the palladium active sites in the palladium carbon (Pd/C) catalyst, so that the hydrogenation activity can be appropriately controlled without using a sulfur substance.
  • Pd/C palladium carbon
  • FIG. 1 shows an electron micrograph of the hydrogenation catalyst of Production Example 1 taken with a scanning transmission electron microscope.
  • FIG. 2 shows a photograph in which a local area in FIG. 1 is enlarged and the metal composition is visualized.
  • FIG. 2 is a monochrome photograph of an image obtained by coloring the positions of Pd and Cu. The color photograph shows that Cu particles are supported near the surface of Pd particles.
  • the cyclic voltammetry method it can be determined by the cyclic voltammetry method that copper is supported on the palladium surface without being alloyed. More specifically, when cyclic voltammetry is performed under conditions in which only copper is eluted from a catalyst in which copper is supported on Pd, the copper-derived peak disappears as the number of cycles increases, leaving only the palladium peak. Since such a tendency cannot occur in an alloy, it confirms that copper is supported on the palladium surface.
  • Measurement conditions for cyclic voltammetry under which only copper is eluted are shown below.
  • Electrolyte: 0.1 mM K2SO4 ( pH 5.75)
  • Measurement temperature Room temperature Number of cycles: 50 times
  • Examples of the carrier that constitutes the hydrogenation reaction catalyst of the present disclosure include alumina, silica, silica-alumina, and carbon carriers. Among these, carbon supports are preferred. Although the origin of the carbon carrier is not particularly limited, for example, wood or coconut charcoal pulverized coal, coal, oil furnace method, lamp black method, channel method, gas furnace method, acetylene decomposition method, thermal method, etc. carbon and the like. These carbons may be steam activated or chemically activated.
  • the carbon carrier As for the carbon carrier, a known method such as tumbling granulation or extrusion molding is used to produce a carbon carrier having a large average particle diameter, or after molding, a carbon carrier having a large average particle diameter is selected by sieving or the like. is also possible.
  • the specific surface area (BET value) of the carrier is not limited, it is preferably 50 to 3000 m 2 /g, more preferably 100 to 1500 m 2 /g.
  • a specific surface area value means the value measured based on the method of JISZ8830:2013.
  • the shape of the carbon support is not limited as long as it is shaped, and may be spherical, cylindrical, or pellet. Among them, a spherical shape is preferable.
  • a carbon carrier may be a commercially available product in addition to the one produced as described above. Examples of commercially available products include activated carbon beads (BAC-MP, average particle diameter 500 ⁇ m, specific surface area value 1200 m 2 /g, spherical shape) sold by Kureha Corporation.
  • the method for supporting palladium on a carrier is not limited, but can be carried out, for example, by dissolving a palladium compound in a solvent, introducing the carrier into the solution, and adsorbing or impregnating the palladium compound.
  • a water-soluble palladium compound such as chloropalladium acid
  • water can be used as a solvent.
  • a water-insoluble palladium compound such as bis(2,4-pentanedionato)palladium
  • an organic solvent that dissolves the palladium compound can be used as the solvent.
  • a commercial product may be used as the palladium carrier on which palladium is supported.
  • Examples of such commercial products include "5% by weight Pd/C catalyst K type” (manufactured by N E Chemcat).
  • the method for supporting copper on palladium is not particularly limited.
  • a copper compound is added to a solution containing carbon on which palladium is supported, and the copper compound is supported on palladium. can.
  • reduction treatment may be performed as necessary.
  • gaseous hydrogen can be used in addition to reducing agents such as methanol, formaldehyde and formic acid.
  • gaseous hydrogen is used, but it is also possible to dilute hydrogen gas with an inert gas such as nitrogen and use it.
  • Copper compounds include, for example, copper formate, copper acetate, copper propionate, copper butyrate, copper valerate, copper caproate, copper enanthate, copper caprylate, copper pelargonate, copper caprate, copper undecylate, lauric acid Copper, copper tridecylate, copper myristate, copper pentadecylate, copper palmitate, copper margarate, copper stearate, copper nonadesylate, copper arachidate, copper heneicosylate, copper behenate, copper tricosylate, copper lignocerate, Copper cerrotate, copper montanate, copper melisinate, copper benzoate, copper oxalate, copper malonate, copper succinate, copper terephthalate, copper isophthalate, copper phthalate, copper salicylate, copper citrate, copper tartrate, etc.
  • Inorganic copper salts such as copper sulfate, copper carbonate, and copper nitrate; Copper halides such as copper iodide, copper bromide, and copper chloride; Copper hydroxides such as copper hydroxide; Copper such as copper oxide oxides.
  • the valence of copper in these copper compounds may be either monovalent or divalent, and two or more copper salts may be used in combination. These copper salts may be hydrates.
  • the copper compound is not particularly limited as long as it contains a copper atom, but from the viewpoint of high solubility in water and polar solvents, for example, copper formate, copper acetate, copper nitrate, copper chloride, copper sulfate, etc. Salts or hydrated salts of divalent organic or inorganic copper ions of are preferred.
  • the solution may be water, a polar solvent, or a non-polar solvent, but water or a polar solvent is preferable, and water is more preferable.
  • the amount of copper supported is not limited, but it preferably contains 10 to 200% by mass, more preferably 15 to 150% by mass, and 20 to 100% by mass with respect to 100% by mass of palladium. is more preferred.
  • the supported amount of copper is set within the above range, it is possible to improve the reaction rate of the hydrogenation reaction while maintaining the functional group selectivity. That is, if the supported amount of copper is too small, the functional group selectivity will decrease. On the other hand, if the supported amount of copper is excessive, copper may cover all the active sites of palladium, preventing the hydrogenation reaction from occurring.
  • the supported amounts of copper and palladium can be calculated as follows. First, the object is immersed in aqua regia to dissolve the metal. Next, carbon, which is an insoluble component, is removed from the aqua regia. Thereafter, by analyzing the aqua regia from which the carbon has been removed by ICP emission spectrometry, the supported amounts of copper and palladium can be calculated.
  • the amount of copper and palladium supported on the hydrogenation reaction catalyst can be adjusted by adjusting the amount of the copper compound added.
  • hydrogenation is selective hydrogenation of nitro groups and/or unsaturated hydrocarbon groups in a plurality of functional groups hydrogenated by the hydrogenation reaction. is preferred.
  • Multiple functional groups hydrogenated by hydrogenation reaction include, for example, a nitro group, an unsaturated hydrocarbon group, an aromatic ketone, an aromatic chlorine atom, a benzyl protective group, a nitrile group, and a benzylic hydroxyl group.
  • Niro group refers to a nitro group bonded to an aliphatic hydrocarbon group, a nitro group bonded to an aromatic ring, or a nitro group bonded to a heterocyclic ring.
  • Unsaturated hydrocarbon group refers to a carbon-carbon double bond or a carbon-carbon triple bond.
  • Aromatic chlorine atom refers to a chlorine atom connected to an aromatic or heterocyclic ring.
  • Benzyl protecting group refers to a benzyl group used as a protecting group for a hydroxyl group or a carboxylic acid group.
  • Benzyl-position hydroxyl group refers to a hydroxyl group that binds to a carbon atom that connects to an aromatic or heterocyclic ring.
  • the hydrogenation reaction catalyst of the present disclosure has only a part of the functional groups and/or unsaturated bonds of the organic compound to be hydrogenated, which has two or more functional groups and/or unsaturated bonds.
  • functional groups and/or some of the unsaturated bonds That is, the hydrogenation site can be selectively hydrogenated.
  • “Functional groups and/or unsaturated bonds that are hydrogenated by a hydrogenation reaction” include, for example, the aforementioned “multiple functional groups that are hydrogenated by a hydrogenation reaction”.
  • non-hydrogenated sites sites not hydrogenated by the hydrogenation reaction
  • examples of non-hydrogenated sites (sites not hydrogenated by the hydrogenation reaction) of the organic compound to be hydrogenated include aromatic ketones, aromatic chlorine atoms, benzyl protective groups, nitrile groups, and benzylic hydroxyl groups.
  • examples of the hydrogenation site of the organic compound to be hydrogenated include a nitro group and an unsaturated hydrocarbon group.
  • the hydrogenation reaction catalyst described above can be produced by bringing Pd/C into contact with a copper salt solution, raising the temperature and stirring, and then washing.
  • the method of bringing Pd/C into contact with the copper salt solution is as described above.
  • the elevated temperature is not limited as long as the copper compound can be dissolved, but is preferably 25 to 100°C, more preferably 35 to 90°C, and even more preferably 50 to 80°C.
  • the stirring time is not limited as long as copper can be supported on palladium, but is preferably 5 to 60 minutes, more preferably 10 to 50 minutes, and even more preferably 20 to 40 minutes.
  • gaseous hydrogen can be used in addition to reducing agents such as methanol, formaldehyde and formic acid.
  • gaseous hydrogen is used, but it is also possible to dilute hydrogen gas with an inert gas such as nitrogen and use it.
  • Washing is not limited, but can be performed, for example, by filtering the stirred solution and applying a solvent to the filtrate.
  • the solvent used for washing is preferably about 0° C. to 25° C., and washing is preferably performed 1 to 3 times.
  • the method for producing a hydrogenation reaction catalyst of the present disclosure preferably does not substantially include sintering under reduction after washing.
  • sintering refers to subjecting the washed material to a temperature at which copper and palladium are alloyed, for example, 700 to 1000° C. at 1 atm. Thus, as long as the copper and palladium do not alloy, for example, they may be heated for drying.
  • Functional groups and/or unsaturated bonds that are selectively hydrogenated include nitro groups and unsaturated hydrocarbon groups, as described above.
  • the method for producing a hydrogenated organic compound of the present disclosure for example, in the field of organic synthesis, in addition to raw materials for gene introduction agents, intermediates for pharmaceuticals and agricultural chemicals, image quality improvers for inkjet inks It is useful as a method for synthesizing various derivatives obtained by hydrogenation of aromatic nitro compounds, which are being studied for use as raw materials for functional polymers such as raw materials for photosensitive polymer compounds.
  • the hydrogenation reaction catalyst of the present disclosure is a catalyst in which palladium/copper is supported on carbon, it can be easily recovered by, for example, filtration after the completion of the hydrogenation reaction. After that, it can be reused.
  • Example 1 Using the hydrogenation reaction catalyst (5% Pd-3% Cu/C) produced in Production Example 1, a hydrogenation reaction represented by the following formula was carried out. Specifically, p-nitroacetophenone was dissolved in 1 ml of ethyl acetate, 10 mg of the hydrogenation reaction catalyst (5% Pd-3% Cu/C) produced in Production Example 1 was added, and hydrogen was dissolved at 0.2 MPa. A hydrogenation reaction was carried out at 60° C. for 2 hours in an atmosphere. The obtained reaction product was analyzed by GC-MS, and its conversion and selectivity were calculated. Table 2 shows the results.
  • the other compound (3) in the reaction formula below is a mixture of compounds other than the starting material (1) and the target compound (2).
  • Examples 2-3> Instead of the hydrogenation reaction catalyst (5% Pd-3% Cu/C) produced in Production Example 1, the hydrogenation reaction catalyst produced in Production Examples 2 and 3 (5% Pd-1.5% Cu/ C) A hydrogenation reaction was carried out in the same manner as in Example 1, except that a hydrogenation reaction catalyst (5% Pd-4.5% Cu/C) was used. The obtained reaction product was analyzed by GC-MS, and its conversion and selectivity were calculated. Table 2 shows the results.
  • Examples 1, 4 to 13> Using the hydrogenation reaction catalyst (5% Pd-3% Cu/C) produced in Production Example 1, a hydrogenation reaction represented by the following formula was carried out. Specifically, the raw materials shown in Table 3 are dissolved in 1 ml of the solvent shown in Table 3, 10 mg of the hydrogenation reaction catalyst (5% Pd-3% Cu/C) produced in Production Example 1 is added, and hydrogen A hydrogenation reaction was carried out at the reaction temperature and reaction time shown in Table 3 under an atmosphere of 0.2 MPa. The obtained reaction product was analyzed by GC-MS, and its conversion and selectivity were calculated. Table 3 shows the results.
  • Example 6 Using the hydrogenation reaction catalyst (5% Pd-3% Cu/C) produced in Production Example 1, the hydrogenation reaction represented by the following reaction formula was carried out. Specifically, o-chloronitrobenzene is dissolved in 1 ml of ethyl acetate, 10 mg of the hydrogenation reaction catalyst (5% Pd-3% Cu/C) produced in Production Example 1 is added, and hydrogen is heated to 0.2 MPa. A hydrogenation reaction was carried out at 60° C. for 2 hours in an atmosphere. The obtained reaction product was analyzed by GC-MS, and its conversion and selectivity were calculated. The results are shown in Tables 4 and 5.
  • the other compound (3) in the reaction formula below is a mixture of compounds other than the starting material (1) and the target compound (2).
  • Example 6 After the hydrogenation reaction in Example 6, the catalyst was recovered by filtering and separating the catalyst from the reaction system. The recovered catalyst was put into the reaction system again and used repeatedly in the hydrogenation reaction. Specifically, instead of the hydrogenation reaction catalyst (5% Pd-3% Cu/C) produced in Production Example 1, the recovered catalyst was used, and the reaction time was shortened to 1 hour. , the hydrogenation reaction was repeated 1 to 4 times in the same manner as in Example 6. The reactants obtained in the first, second, third and fourth hydrogenation reactions were each analyzed by GC-MS, and their conversion and selectivity were calculated. In addition, the catalyst recovered from each hydrogenation reaction was analyzed by ICP-MS (manufactured by Agilent) to measure the amounts of palladium and copper that flowed out into the solvent. Table 4 shows the results.
  • ICP-MS manufactured by Agilent

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Abstract

Le problème décrit par la présente invention est de fournir un catalyseur pour des réactions d'hydrogénation ; ledit catalyseur présente une excellente durabilité de catalyseur et est capable d'hydrogéner sélectivement de façon unique certains groupes fonctionnels et/ou liaisons insaturées d'un composé organique à hydrogéner ; ledit composé organique présente une pluralité de groupes fonctionnels et/ou de liaisons insaturées et a été classiquement hydrogéné par une réaction d'hydrogénation qui utilise un catalyseur au palladium-carbone. La solution selon l'invention consiste en un catalyseur pour des réactions d'hydrogénation qui comprend un support, du palladium qui est chargé sur le support, et du cuivre qui est chargé sur le palladium.
PCT/JP2023/003674 2022-02-04 2023-02-03 Catalyseur pour réactions d'hydrogénation, son procédé de production et procédé de production d'un composé organique hydrogéné Ceased WO2023149559A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI885616B (zh) * 2023-11-30 2025-06-01 國立清華大學 固體銅碳觸媒的製備方法

Citations (5)

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Publication number Priority date Publication date Assignee Title
JPS62149635A (ja) * 1985-12-24 1987-07-03 Mitsubishi Petrochem Co Ltd 選択的水素添加によるスチレン類含有物の精製法
JPH04288028A (ja) * 1990-11-06 1992-10-13 Elf Atochem Sa フルオロエチレン及びクロロフルオロエチレンの製造
WO1993025510A1 (fr) * 1992-06-05 1993-12-23 Daikin Industries, Ltd. Procedes d'obtention de 1,1,1,2,3-pentafluoro-propene et de 1,1,1,2,3-pentafluoro-propane
US20120111802A1 (en) * 2009-05-05 2012-05-10 Technion Research And Development Foundation Ltd. Activated carbon cloth-supported bimetallic pd-cu catalysts for nitrate removal from water
US20170342019A1 (en) * 2013-09-04 2017-11-30 Taminco Bvba Process for the reductive amination and selective hydrogenation of substrates containing a selected halogen

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62149635A (ja) * 1985-12-24 1987-07-03 Mitsubishi Petrochem Co Ltd 選択的水素添加によるスチレン類含有物の精製法
JPH04288028A (ja) * 1990-11-06 1992-10-13 Elf Atochem Sa フルオロエチレン及びクロロフルオロエチレンの製造
WO1993025510A1 (fr) * 1992-06-05 1993-12-23 Daikin Industries, Ltd. Procedes d'obtention de 1,1,1,2,3-pentafluoro-propene et de 1,1,1,2,3-pentafluoro-propane
US20120111802A1 (en) * 2009-05-05 2012-05-10 Technion Research And Development Foundation Ltd. Activated carbon cloth-supported bimetallic pd-cu catalysts for nitrate removal from water
US20170342019A1 (en) * 2013-09-04 2017-11-30 Taminco Bvba Process for the reductive amination and selective hydrogenation of substrates containing a selected halogen

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI885616B (zh) * 2023-11-30 2025-06-01 國立清華大學 固體銅碳觸媒的製備方法

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