Contact hydrogenation reduction method

Abstract

To provide a catalytic hydrogenation reduction method which enables performing a catalytic hydrogenation reduction reaction with a high conversion ratio.SOLUTION: Provided is a catalytic hydrogenation reduction method which causes a reaction substrate and a hydrogen source to contact each other in the presence of a platinum group metal-carrying catalyst to perform catalytic hydrogenation reduction of the reaction substrate, and in which: the platinum group metal-carrying catalyst comprises an ion exchanger carrying at least one of platinum group metal ions, platinum group metal complex ions, and platinum group metal nano particles with an average particle diameter being in a range of 1 to 100 nm; the ion exchanger is a non-particulate weakly basic organic porous ion exchanger comprising a continuous skeleton phase and a continuous pore phase, with a thickness of the continuous skeleton phase in a range of 1-100 μm, an average diameter of the continuous pore phase in a range of 1-1000 μm, a total pore volume in a range of 0.5-50 mL / g, an ion exchange capacity per weight in a dry state in a range of 1-9 mg equivalent / g, and ion exchange groups distributed in the ion exchange body.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a catalytic hydrogenation reduction method using a platinum group metal-supported catalyst.

Background Art

[0002] The catalytic hydrogenation reaction using a heterogeneous catalyst, namely the so-called catalytic reduction reaction, is one of the most important processes in the chemical industry and is widely used in the hydrogenation of aromatic nitro compounds, unsaturated bonds, debenzylation reactions, and the like.

[0003] As heterogeneous catalysts used in the catalytic reduction reaction, catalysts in which platinum group metals typified by palladium are supported on various carriers have been proposed. For example, supported catalysts using inorganic carriers such as activated carbon, zeolite, silica, and alumina as carriers are known. On the other hand, as organic carriers, particulate MR-type weakly basic anion exchange resins (see Patent Document 1), particulate ion exchange resins into which ethylenediamine has been introduced (see Patent Document 2), synthetic adsorbents (see Patent Document 3), non-particulate strongly basic organic porous anion exchangers or non-particulate strongly acidic organic porous cation exchangers (see Patent Document 4), etc. have been disclosed.

[0004] However, the particle diameters of the particulate ion exchange resins and synthetic adsorbents used as carriers in Patent Documents 1 to 3 are usually as large as several hundred μm, so it takes time for the diffusion of the substrate, and furthermore, since the contact efficiency with hydrogen is low, there are problems such as a slow reaction rate, and in the case of a catalyst using a synthetic adsorbent as a carrier, there are problems such as restrictions on the reactions that can be used.

[0005] In addition, although it is described in Patent Document 4 that the ion exchange groups of the non-particulate weakly basic organic porous ion exchangers used as carriers are strongly basic anion groups or strongly acidic cation groups, there is no description of carriers having weakly basic functional groups. Further, for platinum group metal-supported catalysts in which platinum group metal nanoparticles are supported on the non-particulate strongly basic organic porous anion exchangers or non-particulate strongly acidic organic porous cation exchangers described in Patent Document 4, further improvement in catalytic activity is required.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Summary of the Invention

Problems to be Solved by the Invention

[0007] An object of the present invention is to provide a catalytic hydrogenation reduction method capable of performing a catalytic hydrogenation reduction reaction with a high conversion rate.

Means for Solving the Problems

[0008] The present invention is a catalytic hydrogenation reduction method in which a reaction substrate and a hydrogen source are brought into contact in the presence of a platinum group metal-supported catalyst to perform catalytic hydrogenation reduction of the reaction substrate, wherein the platinum group metal-supported catalyst is an ion exchanger on which at least one of platinum group metal ions, platinum group metal complex ions, and platinum group metal nanoparticles having an average particle diameter in the range of 1 to 100 nm is supported, and the ion exchanger is composed of a continuous skeleton phase and a continuous pore phase, the thickness of the continuous skeleton is in the range of 1 to 100 μm, the average diameter of the continuous pores is in the range of 1 to 1000 μm, the total pore volume is in the range of 0.5 to 50 mL / g, the ion exchange capacity per unit weight in the dry state is in the range of 1 to 9 meq / g, and the ion exchange groups are distributed in the ion exchanger Monolith and is a weakly basic organic porous ion exchanger, which is a catalytic hydrogenation reduction method.

[0009] In the catalytic hydrogenation reduction method, the MonolithThe weakly basic organic porous ion exchanger has a continuous macroporous structure in which macropores are interconnected and have a common opening with an average diameter in the range of 1 to 1000 μm within the walls of the macropores. The total pore volume is in the range of 1 to 50 mL / g, and the ion exchange capacity per unit weight in the dry state is in the range of 1 to 9 meq / g. It is preferable that the ion exchange groups are distributed in the organic porous ion exchanger.

[0010] In the catalytic hydrogenation reduction method, the Monolith The weakly basic organic porous ion exchanger is formed by aggregation of organic polymer particles with an average particle diameter in the range of 1 to 50 μm to form a three-dimensionally continuous skeletal portion, and has three-dimensionally continuous pores with an average diameter in the range of 20 to 100 μm between the skeletons. The total pore volume is in the range of 1 to 10 mL / g, and the ion exchange capacity per unit weight in the dry state is in the range of 1 to 9 meq / g. It is preferable that the ion exchange groups are distributed in the organic porous ion exchanger.

[0011] In the catalytic hydrogenation reduction method, the Monolith The weakly basic organic porous ion exchanger is a continuous macroporous structure in which bubble-like macropores overlap, and the overlapping portion forms an opening with an average diameter in the range of 30 to 300 μm. The total pore volume is in the range of 0.5 to 10 mL / g, and the ion exchange capacity per unit weight in the dry state is in the range of 1 to 9 meq / g. The ion exchange groups are distributed in the organic porous ion exchanger, and in the SEM image of the cross-section of the continuous macroporous structure, the area of the skeletal portion appearing in the cross-section is preferably in the range of 25 to 50% of the image area.

[0012] In the catalytic hydrogenation reduction method, the MonolithThe weakly basic organic porous ion exchanger is composed of an aromatic vinyl polymer containing a crosslinked structural unit in the range of 0.1 to 5.0 mol% in all constituent units into which an ion exchange group is introduced, and has a three-dimensionally continuous skeleton with a thickness in the range of 1 to 60 μm. It is a co-continuous structure composed of three-dimensionally continuous pores with an average diameter in the range of 10 to 200 μm between the skeletons. The total pore volume is in the range of 0.5 to 10 mL / g, the ion exchange capacity per unit weight in the dry state is in the range of 1 to 9 meq / g, and it is preferable that the ion exchange groups are distributed in the organic porous ion exchanger.

[0013] In the catalytic hydrogenation reduction method, the Monolith The weakly basic organic porous ion exchanger consists of a continuous skeleton phase and a continuous pore phase. The skeleton has a plurality of particulate bodies with a diameter in the range of 4 to 40 μm adhering to the surface or a plurality of protrusions with a size in the range of 4 to 40 μm formed on the skeleton surface of the organic porous Ion exchange body. The average diameter of the continuous pores is in the range of 10 to 200 μm, the total pore volume is in the range of 0.5 to 10 mL / g, the ion exchange capacity per unit weight in the dry state is in the range of 1 to 9 meq / g, and it is preferable that the ion exchange groups are distributed in the organic porous ion exchanger.

[0014] In the catalytic hydrogenation reduction method, it is preferable that the loading amount of at least one of the platinum group metal ions, the platinum group metal complex ions, and the platinum group metal nanoparticles is in the range of 0.01 to 10% by mass in terms of platinum group metal atoms.

[0015] In the catalytic hydrogenation reduction method, by continuously supplying the reaction substrate and the hydrogen source to the reaction vessel filled with the platinum group metal-supported catalyst, it is preferable to continuously contact the reaction substrate and the hydrogen source in the presence of the platinum group metal-supported catalyst to perform catalytic hydrogenation reduction of the reaction substrate.

Advantages of the Invention

[0016] According to the present invention, it is possible to provide a catalytic hydrogenation reduction method capable of performing a catalytic hydrogenation reduction reaction with a high conversion rate.

Brief Description of the Drawings

[0017]

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Mode for Carrying Out the Invention

[0018] Embodiments of the present invention will be described below. This embodiment is an example of carrying out the present invention, and the present invention is not limited to this embodiment.

[0019] <Catalytic Hydrogenation Reduction Method> The catalytic hydrogenation reduction method according to the embodiment of the present invention is a catalytic hydrogenation reduction method in which a reaction substrate and a hydrogen source are brought into contact in the presence of a platinum group metal-supported catalyst to perform catalytic hydrogenation reduction of the reaction substrate.

[0020] The platinum group metal-supported catalyst is a platinum group metal-supported catalyst in which at least one of platinum group metal ions, platinum group metal complex ions, and platinum group metal nanoparticles having an average particle diameter in the range of 1 to 100 nm is supported on an ion exchanger. The ion exchanger is composed of a continuous skeleton phase and a continuous pore phase. The thickness of the continuous skeleton is in the range of between 1 and 100 μm, the average diameter of the continuous pores is in the range of 1 to 1000 μm, the total pore volume is in the range of 0.5 to 50 mL / g, the ion exchange capacity per weight in the dry state is in the range of 1 to 9 meq / g, and it is a non-particulate weakly basic organic porous ion exchanger in which ion exchange groups are distributed in the ion exchanger.

[0021] Hereinafter, "at least one of platinum group metal ions, platinum group metal complex ions, and platinum group metal nanoparticles having an average particle diameter in the range of 1 to 100 nm" may be referred to as "platinum group metal etc.".

[0022] As a result of intensive studies by the present inventors, in the presence of a platinum group metal-supported catalyst in which a platinum group metal or the like is supported on a non-particulate weakly basic organic porous ion exchanger, a reaction substrate and a hydrogen source are brought into contact with each other to carry out catalytic hydrogenation reduction of the reaction substrate, whereby it has been found that a catalytic hydrogenation reduction reaction can be carried out at a high conversion rate. Since a catalytic hydrogenation reduction reaction can be carried out at a high conversion rate, the amount of the catalyst used can be reduced as compared with the case where the conversion rate is low, and the amount of the platinum group metal used can be reduced. Further, the platinum group metal-supported catalyst in which a platinum group metal or the like is supported on a non-particulate weakly basic organic porous ion exchanger has a long catalyst life.

[0023] [Non-particulate weakly basic organic porous ion exchanger] In the platinum group metal-supported catalyst used in the catalytic hydrogenation reduction method according to the present embodiment, the carrier on which a platinum group metal or the like is supported is a non-particulate weakly basic organic porous ion exchanger. The non-particulate weakly basic organic porous ion exchanger is obtained by introducing a weakly basic ion exchange group into a monolithic organic porous body having a continuous skeleton phase and a continuous pore phase. The monolithic organic porous body has a large number of communication pores serving as flow paths between the skeletons. In the present specification, the "monolithic organic porous body" is simply referred to as "monolith", the "weakly basic monolithic organic porous ion exchanger" is simply referred to as "monolith ion exchanger" or "monolith anion exchanger", and the "monolithic organic porous intermediate" which is an intermediate (precursor) in the production of the monolith is also simply referred to as "monolith intermediate".

[0024] The structure of this non-particulate weakly basic organic porous ion exchanger is disclosed in JP-A Nos. 2002-306976, 2009-007550, 2009-062512, 2009-067982, and 2009-108294.

[0025] The non-particulate weakly basic organic porous ion exchanger consists of a continuous skeletal phase and a continuous pore phase. The thickness of the continuous skeleton ranges from 1 to 100 μm, the average diameter of the continuous pores ranges from 1 to 1000 μm, the total pore volume ranges from 0.5 to 50 mL / g, the ion exchange capacity per weight in the dry state ranges from 1 to 9 meq / g, and the ion exchange groups are distributed in the organic porous ion exchanger. The continuous skeletal phase and the continuous pore phase are observed by SEM images.

[0026] The thickness of the continuous skeleton of the non-particulate weakly basic organic porous ion exchanger in the dry state ranges from 1 to 100 μm. The thickness of the continuous skeleton of the non-particulate weakly basic organic porous ion exchanger in the dry state is determined by SEM observation. When the thickness of this continuous skeleton is less than 1 μm, the ion exchange capacity per volume may decrease, or the mechanical strength may decrease. When filling the platinum group metal-supported catalyst into the reaction vessel and passing the reaction liquid through, especially when passing the liquid at a high flow rate, the non-particulate weakly basic organic porous ion exchanger may be deformed. When the thickness of this continuous skeleton exceeds 100 μm, the skeleton may become too thick, and the pressure loss during liquid passage may increase.

[0027] The average diameter of the continuous pores of the non-particulate weakly basic organic porous ion exchanger in the dry state ranges from 1 to 1000 μm. The average diameter of the continuous pores of the non-particulate weakly basic organic porous ion exchanger in the dry state is measured by the mercury intrusion method and refers to the maximum value of the pore size distribution curve obtained by the mercury intrusion method. When the average diameter of this continuous pore is less than 1 μm, when filling the platinum group metal-supported catalyst into the reaction vessel and passing the reaction liquid through, the pressure loss during liquid passage may increase. When the average diameter of this continuous pore exceeds 1000 μm, when filling the platinum group metal-supported catalyst into the reaction vessel and passing the reaction liquid through, the contact between the reaction liquid and the monolithic ion exchanger may be insufficient, and the catalytic activity may decrease.

[0028] The total pore volume of the non-particulate weakly basic organic porous ion exchanger in the dry state is in the range of 0.5 to 50 mL / g. The total pore volume of the non-particulate weakly basic organic porous ion exchanger in the dry state is measured by the mercury intrusion method. If this total pore volume is less than 0.5 mL / g, when filling the reaction vessel with the platinum group metal-supported catalyst and passing the reaction solution through it, the pressure loss during liquid passage may become large. If this total pore volume exceeds 50 mL / g, the mechanical strength of the non-particulate weakly basic organic porous ion exchanger decreases, and when filling the reaction vessel with the platinum group metal-supported catalyst and passing the reaction solution through it, especially when passing the liquid at a high flow rate, the monolith ion exchanger may be deformed and the pressure loss during liquid passage may increase.

[0029] The ion exchange capacity per unit weight of the non-particulate weakly basic organic porous ion exchanger in the dry state is in the range of 1 to 9 meq / g. The ion exchange capacity per unit weight of the non-particulate weakly basic organic porous ion exchanger in the dry state is measured by methods such as neutralization titration and precipitation titration. If this ion exchange capacity is less than 1 meq / g, the amount of platinum group metal ions or platinum group metal complex ions that can be supported may decrease. If this ion exchange capacity exceeds 9 meq / g, the ion exchange group introduction reaction becomes severe, and the oxidative degradation of the monolith may progress significantly.

[0030] In the non-particulate weakly basic organic porous ion exchanger, the introduced ion exchange groups are preferably distributed not only on the surface of the monolith but also inside the monolith skeleton, that is, in the organic porous ion exchanger, and more preferably evenly distributed. "The ion exchange groups are evenly distributed in the organic porous ion exchanger" means that the distribution of the ion exchange groups is at least on the order of μm and is distributed on the surface and inside the skeleton of the organic porous ion exchanger. The distribution status of the ion exchange groups is confirmed by using an electron probe microanalyzer (EPMA). When the ion exchange groups are distributed not only on the surface of the monolith but also inside the monolith skeleton, the physical and chemical properties of the surface and inside of the monolith can be made substantially uniform, so the durability against swelling and shrinkage is improved.

[0031] The ion exchange groups introduced into the non-particulate weakly basic organic porous ion exchanger are weakly basic anion exchange groups. Examples of the weakly basic anion exchange groups include tertiary amino groups such as dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, methylhydroxyethylamino group, methylhydroxypropylamino group, dicyclohexylamino group, pyrrolidyl group, piperidyl group, 2,2,6,6-tetramethylpiperidyl group, morpholyl group, secondary amino groups such as methylamino group, ethylamino group, propylamino group, butylamino group, hydroxyethylamino group, hydroxybutylamino group, and primary amino groups.

[0032] In the non-particulate weakly basic organic porous ion exchanger, the material constituting the continuous skeleton is an organic polymer material having a crosslinked structure. It is preferable that the crosslinked structure units are contained in an amount of 0.1 to 30 mol% based on all the constituent units constituting the organic polymer material, and more preferably 0.1 to 20 mol%.

[0033] There is no particular limitation on the type of the organic polymer material. For example, aromatic vinyl polymers such as polystyrene, poly(α-methylstyrene), polyvinyltoluene, polyvinylbenzyl chloride, polyvinylbiphenyl, and polyvinylnaphthalene; polyolefins such as polyethylene and polypropylene; poly(halogenated polyolefins) such as polyvinyl chloride and polytetrafluoroethylene; nitrile polymers such as polyacrylonitrile; crosslinked polymers such as (meth)acrylic polymers such as polymethyl methacrylate, polyglycidyl methacrylate, and polyethyl acrylate. The organic polymer material may be a polymer obtained by copolymerizing a single vinyl monomer and a crosslinking agent, or a polymer obtained by polymerizing a plurality of vinyl monomers and a crosslinking agent, or a blend of two or more polymers. Among these organic polymer materials, a crosslinked polymer of an aromatic vinyl polymer is preferable in terms of ease of forming a continuous structure, ease of introducing an ion exchange group, high mechanical strength, and high stability against acids or alkalis. In particular, a styrene-divinylbenzene copolymer or a vinylbenzyl chloride-divinylbenzene copolymer is mentioned as a preferable material.

[0034] [First to Fifth Monolithic Ion Exchangers] As more specific embodiments of the non-particulate weakly basic organic porous ion exchanger, for example, the following first monolithic organic porous ion exchanger (monolithic ion exchanger) to fifth monolithic organic porous ion exchanger (monolithic ion exchanger) can be mentioned. In the following description, the description of the same configuration as that of the above non-particulate weakly basic organic porous ion exchanger will be omitted.

[0035] (First Monolithic Ion Exchanger) The first monolithic ion exchanger has a continuous macroporous structure with macropores connected to each other and common openings (mesopores) with an average diameter in the range of 1 to 1000 μm within the walls of the macropores. The total pore volume is in the range of 1 to 50 mL / g, and the ion exchange capacity per weight in the dry state is in the range of 1 to 9 meq / g. The ion exchange groups are distributed in the organic porous ion exchanger, which is a monolithic ion exchanger.

[0036] As shown in FIG. 1, the first monolithic ion exchanger is a continuous macroporous structure having continuous macropores (pores). The first monolithic ion exchanger and its manufacturing method are disclosed in JP-A-2002-306976.

[0037] The first monolithic ion exchanger has macropores connected to each other and common openings (mesopores) located within the walls of the macropores. The mesopores have overlapping portions where the macropores overlap. The overlapping portion of the mesopores preferably has an average diameter in the range of 1 to 1000 μm in the dry state, more preferably in the range of 10 to 200 μm, and even more preferably in the range of 20 to 200 μm. The average diameter of the openings of the first monolith in the dry state is measured by the mercury intrusion method and refers to the maximum value of the pore size distribution curve obtained by the mercury intrusion method.

[0038] Most of such a first monolithic ion exchanger has an open pore structure in which the voids formed by macropores and mesopores serve as flow channels. When the average diameter of the overlapping part of the mesopores in the dry state is less than 1 μm, when filling a reaction vessel with a platinum group metal-supported catalyst and passing a reaction liquid through it, the pressure loss during liquid flow may become extremely large. When the average diameter of the overlapping part of the mesopores in the dry state exceeds 1000 μm, when filling a reaction vessel with a platinum group metal-supported catalyst and passing a reaction liquid through it, the contact between the reaction liquid and the monolithic ion exchanger may become insufficient, and the catalytic activity may decrease. The overlap of macropores and macropores is, for example, 1 to 12 in one macropore, and many are 3 to 10. Since the first monolithic ion exchanger is the above-described continuous macroporous structure, it is possible to form groups of macropores and groups of common pores almost uniformly, and compared with a particle-aggregated porous body as described in Japanese Patent Application Laid-Open No. 8-252579, etc., the pore volume and specific surface area can be significantly increased.

[0039] The total pore volume per unit weight of the first monolithic ion exchanger in the dry state is preferably in the range of 1 to 50 mL / g, and more preferably in the range of 2 to 30 mL / g. When the total pore volume per unit weight in the dry state is less than 1 mL / g, when filling a reaction vessel with a platinum group metal-supported catalyst and passing a reaction liquid through it, the pressure loss during liquid flow may increase, and furthermore, the permeation amount per unit cross-sectional area may decrease, and the processing capacity may decrease. When the total pore volume per unit weight in the dry state exceeds 50 mL / g, the mechanical strength decreases, and when filling a reaction vessel with a platinum group metal-supported catalyst and passing a reaction liquid through it, the monolithic ion exchanger may be deformed particularly when flowing at a high flow rate.

[0040] The ion exchange capacity per unit weight in the dry state is as described above. Also, "the ion exchange groups are distributed in the organic porous ion exchanger" is as described above.

[0041] (Method for producing the first monolithic ion exchanger) The first monolithic ion exchanger can be produced, for example, by the following method.

[0042] For example, first, an oil-soluble monomer without an ion-exchange group, a surfactant, water, and, if necessary, a polymerization initiator are mixed to obtain a water-in-oil emulsion. Next, this water-in-oil emulsion can be polymerized to form the first monolith.

[0043] The oil-soluble monomer without an ion-exchange group used in the production of the first monolith refers to a monomer that does not contain an ion-exchange group, has low solubility in water, and is lipophilic. Such monomers include, for example, styrene, α-methylstyrene, vinylbenzyl chloride, ethylene, propylene, vinyl chloride, vinyl bromide, acrylonitrile, methacrylonitrile, vinyl acetate, methyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, butanediol diacrylate, methyl methacrylate, ethyl methacrylate, 2-ethylhexyl methacrylate, ethylene glycol dimethacrylate, etc. These monomers can be used alone or in combination of two or more. However, it is preferable to select at least one component of the oil-soluble monomer as a crosslinkable monomer such as divinylbenzene or ethylene glycol dimethacrylate, and set its content in the total oil-soluble monomers in the range of, for example, 0.3 to 10 mol%, preferably in the range of 0.3 to 5 mol%, because it is possible to quantitatively introduce an ion-exchange group in a later step and ensure practically sufficient mechanical strength.

[0044] The surfactant used in the production of the first monolith may be any surfactant that can form a water-in-oil (W / O) emulsion when an oil-soluble monomer containing no ion-exchange group is mixed with water, and there are no particular restrictions. Examples of the surfactant include nonionic surfactants such as sorbitan monooleate, sorbitan monolaurate, and polyoxyethylene nonyl phenyl ether; anionic surfactants such as potassium oleate, sodium dodecylbenzenesulfonate, and sodium dioctyl sulfosuccinate; cationic surfactants such as distearyldimethylammonium chloride; and amphoteric surfactants such as lauryldimethylbetaine. These surfactants can be used alone or in combination of two or more. A water-in-oil emulsion refers to an emulsion in which the oil phase is the continuous phase and water droplets are dispersed therein. The addition amount of the surfactant may be, for example, in the range of about 2 to 70% with respect to the total amount of the oil-soluble monomer and the surfactant. In order to control the bubble shape and size of the monolith, alcohols such as methanol and stearyl alcohol; carboxylic acids such as stearic acid; hydrocarbons such as octane, dodecane, and toluene; and cyclic ethers such as tetrahydrofuran and dioxane can also coexist in the system.

[0045] In the production of the first monolith, when forming the monolith by polymerization, the polymerization initiator that is used as needed is preferably a compound that generates radicals by heat and light irradiation. The polymerization initiator may be water-soluble or oil-soluble, and examples thereof include azobisisobutyronitrile, azobisdimethylvaleronitrile, azobiscyclohexanenitrile, azobiscyclohexanecarbonitrile, benzoyl peroxide, potassium persulfate, ammonium persulfate, hydrogen peroxide-ferrous chloride, sodium persulfate-sodium bisulfite, and tetramethylthiuram disulfide. However, in some cases, there are systems in which polymerization proceeds only by heating or only by light irradiation without adding a polymerization initiator, and in such systems, it is not necessary to add a polymerization initiator.

[0046] In the production of the first monolith, the polymerization conditions for polymerizing the water-in-oil emulsion can be variously selected depending on the type of monomer, initiator system, etc. When using, for example, azobisisobutyronitrile, benzoyl peroxide, potassium persulfate, etc. as a polymerization initiator, for example, in a sealed container under an inert atmosphere, it may be heated and polymerized at, for example, 30 to 100 °C for 1 to 48 hours. When using hydrogen peroxide-ferrous chloride, sodium persulfate-sodium acid sulfite, etc. as a polymerization initiator, for example, in a sealed container under an inert atmosphere, it may be polymerized at, for example, 0 to 30 °C for 1 to 48 hours. After the polymerization is completed, the content is taken out and Soxhlet extracted with a solvent such as isopropanol to remove unreacted monomers and residual surfactants, and the first monolith can be obtained.

[0047] As a method for introducing an ion exchange group into the first monolith, for example, there are the following methods (1) and (2). (1) Instead of a monomer containing no ion exchange group, a monomer containing an ion exchange group, for example, a monomer in which an ion exchange group is introduced into the above oil-soluble monomer containing no ion exchange group, can be used for polymerization to obtain a monolith ion exchanger in one step. (2) A monomer containing no ion exchange group can be used for polymerization to form the first monolith, and then an ion exchange group can be introduced.

[0048] The method for introducing an ion exchange group into the first monolith is not particularly limited, and known methods such as polymer reactions and graft polymerization can be used. For example, as a method for introducing an amine group, if the monolith is a styrene-divinylbenzene copolymer, etc., after introducing a chloromethyl group with chloromethyl methyl ether, etc., it is reacted with a desired secondary amine for introduction; a method of producing the monolith by copolymerization of chloromethylstyrene and divinylbenzene and reacting it with a desired secondary amine for introduction; a method of introducing a radical initiation group or a chain transfer group into the monolith, graft polymerizing glycidyl methacrylate, and then reacting it with a desired secondary amine for introduction, etc. can be mentioned.

[0049] (Second monolith ion exchanger) The second monolithic ion exchanger is formed by aggregation of organic polymer particles with an average particle diameter in the range of 1 to 50 μm to form a three-dimensionally continuous skeletal portion, and has three-dimensionally continuous pores with an average diameter in the range of 20 to 100 μm between the skeletons. The total pore volume is in the range of 1 to 10 mL / g, and the ion exchange capacity per unit weight in the dry state is in the range of 1 to 9 meq / g. The ion exchange groups are distributed in the organic porous ion exchanger, which is a monolithic ion exchanger.

[0050] As shown in FIG. 2, the second monolithic ion exchanger is a particle-aggregated structure in which particles are aggregated. The second monolithic ion exchanger and its manufacturing method are disclosed in JP-A-2009-007550.

[0051] The second monolithic ion exchanger has a three-dimensionally continuous skeletal portion formed by aggregation of organic polymer particles having a crosslinked structural unit with an average particle diameter preferably in the range of 1 to 50 μm, more preferably in the range of 1 to 30 μm, in the dry state. The second monolithic ion exchanger has three-dimensionally continuous pores (continuous pores) with an average diameter preferably in the range of 20 to 100 μm, more preferably in the range of 20 to 90 μm, in the dry state, between the continuous skeletons. An SEM photograph of an arbitrarily extracted portion of the cross section of the second monolithic ion exchanger in the dry state is taken, and the diameters of the organic polymer particles of all the particles in the SEM photograph are measured, and their average value is taken as the average particle diameter. The average diameter of the continuous pores in the dry state is determined by the mercury intrusion method, similar to the first monolithic ion exchanger.

[0052] When the average particle diameter of the organic polymer particles is less than 1 μm in the dry state, the average diameter of the continuous pores between the skeletons may become less than 20 μm in the dry state. When the average particle diameter of the organic polymer particles exceeds 50 μm, when the platinum group metal-supported catalyst is filled in the reaction vessel and the reaction solution is passed through, the pressure loss may become large. Further, when the average diameter of the above-mentioned continuous pores is less than 20 μm in the dry state, when the platinum group metal-supported catalyst is filled in the reaction vessel and the reaction solution is passed through, the pressure loss when the reaction solution is permeated may become large. When the average diameter of the above-mentioned continuous pores exceeds 100 μm in the dry state, when the platinum group metal-supported catalyst is filled in the reaction vessel and the reaction solution is passed through, the contact between the reaction solution and the monolith ion exchanger may become insufficient.

[0053] The total pore volume per unit weight of the second monolith ion exchanger in the dry state is preferably in the range of 1 to 10 mL / g. When the total pore volume is less than 1 mL / g, when the platinum group metal-supported catalyst is filled in the reaction vessel and the reaction solution is passed through, the pressure loss during liquid passing may become large. Further, the permeation amount per unit cross-sectional area may become small, and the processing capacity may decrease. When the total pore volume exceeds 10 mL / g, the mechanical strength decreases, and when the platinum group metal-supported catalyst is filled in the reaction vessel and the reaction solution is passed through, the monolith ion exchanger may be deformed particularly when passing the liquid at a high flow rate.

[0054] The ion exchange capacity per unit weight in the dry state is as described above. Also, "the ion exchange groups are distributed in the organic porous ion exchanger" is as described above.

[0055] (Method for producing the second monolith ion exchanger) The second monolith ion exchanger can be produced, for example, by the following method.

[0056] For example, a second monolith can be obtained by mixing a vinyl monomer, a specific amount of a cross-linking agent, an organic solvent, and a polymerization initiator and polymerizing this in a static state.

[0057] The vinyl monomer used for the production of the second monolith is the same as the monomer used for the production of the first monolith.

[0058] The crosslinking agent used for the production of the second monolith preferably contains at least two polymerizable vinyl groups in the molecule and has high solubility in an organic solvent. Examples of the crosslinking agent include divinylbenzene, divinylbiphenyl, and ethylene glycol dimethacrylate. These crosslinking agents can be used alone or in combination of two or more. Preferred crosslinking agents are aromatic polyvinyl compounds such as divinylbenzene, divinylnaphthalene, and divinylbiphenyl in terms of high mechanical strength and stability against hydrolysis. The amount of the crosslinking agent used relative to the total amount of the vinyl monomer and the crosslinking agent ({crosslinking agent / (vinyl monomer + crosslinking agent)} × 100) is, for example, in the range of 1 to 5 mol%, preferably in the range of 1 to 4 mol%.

[0059] The organic solvent used for the production of the second monolith is an organic solvent that dissolves the vinyl monomer and the crosslinking agent but hardly dissolves the polymer formed by the polymerization of the vinyl monomer. In other words, it is a poor solvent for the polymer formed by the polymerization of the vinyl monomer. Examples of this organic solvent include alcohols such as methanol, butanol, and octanol when the vinyl monomer is styrene; chain ethers such as diethyl ether and ethylene glycol dimethyl ether; and chain saturated hydrocarbons such as hexane, octane, and decane.

[0060] The polymerization initiator used for the production of the second monolith is preferably a compound that generates radicals by heat and light irradiation. The polymerization initiator is preferably oil-soluble. The polymerization initiator is, for example, 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), dimethyl 2,2'-azobisisobutyrate, 4,4'-azobis(4-cyanovaleric acid), 1,1'-azobis(cyclohexane-1-carbonitrile), benzoyl peroxide, lauroyl peroxide, potassium persulfate, ammonium persulfate, tetramethylthiuram disulfide, etc. The amount of the polymerization initiator used relative to the total amount of the vinyl monomer and the crosslinking agent ({polymerization initiator / (vinyl monomer + crosslinking agent)} × 100) is, for example, in the range of about 0.01 to 5 mol%.

[0061] In the production of the second monolith, when, for example, 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), benzoyl peroxide, lauroyl peroxide, potassium persulfate, etc. are used as the polymerization initiator, for example, in a sealed container under an inert atmosphere, it may be heat-polymerized at, for example, 30 to 100 °C for 1 to 48 hours. After the polymerization is completed, the content is taken out, and for the purpose of removing the unreacted vinyl monomer and the organic solvent, for example, it can be extracted with a solvent such as acetone to obtain the second monolith.

[0062] In the production of the second monolith, organic polymer particles with an average particle diameter of 1 to 50 μm can be aggregated by adjusting polymerization conditions such as increasing the crosslinking agent, increasing the monomer concentration, and raising the temperature. By setting the amount of the crosslinking agent used relative to the total amount of the vinyl monomer and the crosslinking agent to a specific amount, three-dimensionally continuous pores with an average diameter of 20 to 100 μm can be formed between the skeletons. By polymerizing under conditions such that the amount of the organic solvent used ({organic solvent / (organic solvent + monomer + crosslinking agent)} × 100) relative to the total amount of the organic solvent, monomer, and crosslinking agent used is, for example, in the range of 30 to 80% by weight, preferably in the range of 40 to 70% by weight, the total pore volume of the monolith can be made 1 to 5 mL / g.

[0063] The method for introducing an ion-exchange group into the second monolith is the same as the method for introducing an ion-exchange group into the first monolith.

[0064] (The third monolith ion exchanger) The third monolith ion exchanger is a continuous macroporous structure in which bubble-like macropores overlap with each other and the overlapping part becomes an opening in the range of an average diameter of 30 to 300 μm. The total pore volume is in the range of 0.5 to 10 mL / g, the ion-exchange capacity per weight in the dry state is in the range of 1 to 9 meq / g, the ion-exchange groups are distributed in the organic porous ion exchanger, and in the SEM image of the cross-section of the continuous macroporous structure, the area of the skeleton part appearing in the cross-section is in the range of 25 to 50% in the image area. It is a monolith ion exchanger.

[0065] As shown in FIG. 3, the third monolith ion exchanger is a continuous macroporous structure similar to the first monolith ion exchanger. The third monolith ion exchanger and its production method are disclosed in JP-A-2009-062512.

[0066] The continuous pores have overlapping portions where the macropores overlap each other. The overlapping portion preferably has an average diameter in the range of 30 to 300 μm, more preferably in the range of 30 to 200 μm, and even more preferably in the range of 40 to 100 μm in the dry state. This average diameter is measured by the mercury intrusion method and refers to the maximum value of the pore size distribution curve obtained by the mercury intrusion method. If the average diameter of the openings in the dry state is less than 30 μm, when filling the reaction vessel with the platinum group metal-supported catalyst and passing the reaction liquid through, the pressure loss during liquid passage may become large. If it exceeds 300 μm, the contact between the reaction liquid and the monolithic ion exchanger may be insufficient.

[0067] In the third monolithic ion exchanger, in the SEM image of the cross-section of the continuous macroporous structure in the dry state, the area of the skeleton portion appearing on the cross-section is in the range of, for example, 25 to 50% in the image area, preferably in the range of 25 to 45%. If the area of the skeleton portion appearing on the cross-section is less than 25% in the image area, the skeleton becomes thin, the mechanical strength decreases, and when filling the reaction vessel with the platinum group metal-supported catalyst and passing the reaction liquid through, especially when passing the liquid at a high flow rate, the monolithic ion exchanger may be deformed. If the area of the skeleton portion appearing on the cross-section exceeds 50% in the image area, the skeleton becomes too thick, and when filling the reaction vessel with the platinum group metal-supported catalyst and passing the reaction liquid through, the pressure loss during liquid passage may increase.

[0068] The conditions for obtaining SEM images only need to be those under which the skeletal parts appearing on the cross-section of the cut surface are clearly shown. For example, the magnification is 100 - 600, and the photo area is about 150 mm × 100 mm. The SEM observation is preferably carried out with three or more images taken at different cutting or shooting locations on an arbitrary cut surface of the third monolithic ion exchanger excluding subjectivity. The third monolithic ion exchanger to be cut is in a dry state. The skeletal parts on the cut surface in the SEM image will be described with reference to FIGS. 3 and 4. In FIGS. 3 and 4, those generally with an irregular shape and appearing in cross-section are the "skeletal parts appearing in the cross-section (reference numeral 12)". The circular holes shown in FIG. 3 are openings (mesopores), and those with a relatively large curvature or curved surface are macropores (reference numeral 13 in FIG. 4). The area of the skeletal parts appearing in the cross-section of FIG. 4 is 28% in the rectangular image area 11.

[0069] As a method for measuring the area of the skeletal parts appearing in the cross-section of the cut surface in the SEM image, after identifying the skeletal parts by performing known computer processing or the like, calculation methods by automatic calculation or manual calculation using a computer or the like can be mentioned. As manual calculation, a method of replacing an irregular-shaped object with an aggregate of quadrilaterals, triangles, circles, trapezoids, etc., and stacking them to obtain the area can be mentioned.

[0070] The total pore volume per unit weight of the third monolithic ion exchanger in the dry state is preferably in the range of 0.5 - 10 mL / g, more preferably in the range of 0.8 - 8 mL / g. When the total pore volume is less than 0.5 mL / g, when filling a platinum group metal-supported catalyst into a reaction vessel and passing a reaction liquid through it, the pressure loss during liquid passing may become large. Furthermore, the amount of permeating fluid per unit cross-sectional area may become small, and the processing capacity may decrease. When the total pore volume exceeds 10 mL / g, the mechanical strength decreases, and when filling a platinum group metal-supported catalyst into a reaction vessel and passing a reaction liquid through it, especially when passing the liquid at a high flow rate, the monolithic ion exchanger may be deformed. Furthermore, the contact efficiency between the reaction liquid and the monolithic ion exchanger may decrease.

[0071] The ion exchange capacity per unit weight in the dry state is as described above. Also, the fact that "the ion exchange groups are distributed in the organic porous ion exchanger" is as described above.

[0072] (Method for Producing the Third Monolithic Ion Exchanger) The third monolithic ion exchanger can be produced, for example, by the following method.

[0073] For example, first, an oil-in-water emulsion is prepared by stirring a mixture of an oil-soluble monomer not containing an ion exchange group, a surfactant, and water. Next, the third monolith can be obtained by performing the following Step I, Step II, and Step III. In Step I, the oil-in-water emulsion is polymerized to obtain a monolithic organic porous intermediate having a continuous macropore structure with a total pore volume in the range of, for example, 5 to 16 mL / g (hereinafter also referred to as the monolith intermediate (3)). In Step II, a mixture containing a vinyl monomer, a crosslinking agent having at least two or more vinyl groups in one molecule, an organic solvent in which the vinyl monomer and the crosslinking agent dissolve but the polymer produced by the polymerization of the vinyl monomer does not dissolve, and a polymerization initiator is prepared. In Step III, the mixture obtained in Step II is polymerized in the presence of the monolith intermediate (3) obtained in Step I under static conditions to obtain a third monolith having a thicker skeleton than the skeleton of the monolith intermediate (3).

[0074] Step I is the same as the method for producing the first monolithic ion exchanger.

[0075] The monolith intermediate (3) obtained in Step I has a continuous macropore structure. When this is allowed to coexist in the polymerization system, a porous structure having a thick skeleton can be formed using the structure of the monolith intermediate (3) as a mold. The crosslink density of the polymer material preferably contains crosslinked structural units in the range of, for example, 0.3 to 10 mol%, preferably 0.3 to 5 mol%, based on all the constitutional units constituting the polymer material of the monolith intermediate (3).

[0076] The total pore volume per weight of the monolithic intermediate (3) obtained in Step I in the dry state is, for example, in the range of 5 to 16 mL / g, preferably in the range of 6 to 16 mL / g. To make the total pore volume of the monolithic intermediate (3) within the above numerical range, the ratio of monomer to water may be, for example, in the range of approximately 1:5 to 1:20.

[0077] The monolithic intermediate (3) obtained in Step I has an average diameter of openings (mesopores), which are the overlapping parts of macropores, in the dry state in the range of, for example, 20 to 200 μm.

[0078] Step II is a step of preparing a mixture containing a vinyl monomer, a crosslinking agent having at least two or more vinyl groups in one molecule, an organic solvent in which the vinyl monomer and the crosslinking agent dissolve but the polymer produced by the polymerization of the vinyl monomer does not dissolve, and a polymerization initiator. The order of Step I and Step II may be either one first.

[0079] The vinyl monomer used in Step II may be any lipophilic vinyl monomer containing a polymerizable vinyl group in the molecule and having high solubility in the organic solvent, and it is preferable to select a vinyl monomer that produces the same type or a similar polymer material as the monolithic intermediate (3) coexisting in the above polymerization system. Specific examples of these vinyl monomers are the same as those used in the production of the first monolith.

[0080] The addition amount of the vinyl monomer used in Step II is, with respect to the monolithic intermediate (3) coexisting during the polymerization, in the range of, for example, 3 to 50 times by weight, preferably in the range of 4 to 40 times by weight.

[0081] The crosslinking agent used in Step II is the same as the crosslinking agent used in the production of the second monolith.

[0082] The organic solvent used in Step II is the same as the organic solvent used in the production of the second monolith. The amount of these organic solvents used is preferably such that the concentration of the above vinyl monomer is, for example, 30 to 80% by weight.

[0083] The polymerization initiator used in the II process is the same as the polymerization initiator used in the production of the second monolith.

[0084] In the III process, for example, the mixture obtained in the II process is polymerized under standing and in the presence of the monolith intermediate (3) obtained in the I process, and a third monolith having a skeleton thicker than that of the monolith intermediate (3) can be obtained. When the monolith intermediate (3) with a continuous macroporous structure is present in the polymerization system, a third monolith can be obtained.

[0085] In the III process, for example, in a reaction vessel, the monolith intermediate (3) is placed in a state of being impregnated with a mixture (solution). The mixing ratio of the mixture obtained in the II process and the monolith intermediate (3) may be, for example, adjusted so that the addition amount of the vinyl monomer is in the range of 3 to 50 times by weight, preferably 4 to 40 times by weight, based on the monolith intermediate (3). In the reaction vessel, the vinyl monomer and the crosslinking agent in the mixture are adsorbed and distributed on the skeleton of the standing monolith intermediate, and polymerization proceeds within the skeleton of the monolith intermediate (3).

[0086] In the III process, the polymerization conditions are variously selected depending on the type of monomer, the type of polymerization initiator, etc. For example, when 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), benzoyl peroxide, lauroyl peroxide, potassium persulfate, etc. are used as the polymerization initiator, for example, in a sealed container under an inert atmosphere, it may be heated and polymerized at 30 to 100 °C for 1 to 48 hours. By heat polymerization, the vinyl monomer and the crosslinking agent adsorbed and distributed on the skeleton of the monolith intermediate (3) polymerize within the skeleton, and the skeleton can be thickened. After the polymerization is completed, the content is taken out, and for the purpose of removing the unreacted vinyl monomer and the organic solvent, for example, it can be extracted with a solvent such as acetone to obtain the third monolith.

[0087] The third monolithic ion exchanger can be obtained, for example, by performing a step IV of introducing an ion exchange group into the third monolith obtained in step III. The method of introducing an ion exchange group into the third monolith is the same as the method of introducing an ion exchange group into the first monolith.

[0088] (The fourth monolithic ion exchanger) The fourth monolithic ion exchanger is a co-continuous structure composed of a three-dimensionally continuous skeleton with a thickness in the range of 1 to 60 μm of a continuous skeleton composed of an aromatic vinyl polymer containing a cross-linked structural unit in the range of 0.1 to 5.0 mol% in all the structural units into which an ion exchange group is introduced, and three-dimensionally continuous pores with an average diameter in the range of 10 to 200 μm between the skeletons. The total pore volume is in the range of 0.5 to 10 mL / g, the ion exchange capacity per weight in the dry state is in the range of 1 to 9 meq / g, and it is a monolithic ion exchanger in which the ion exchange groups are distributed in the organic porous ion exchanger.

[0089] As shown in FIGS. 5 and 6, the fourth monolithic ion exchanger has a continuous skeleton phase 1 (continuous skeleton) and a continuous pore phase 2 (continuous pores), and they are intertwined to form a co-continuous structure 10 that is three-dimensionally continuous together. The pore phase 2 has higher continuity and almost no bias in its size compared to the above-described first and second monoliths. The fourth monolithic ion exchanger is considered to have high mechanical strength because its skeleton is thick. The fourth monolithic ion exchanger and its manufacturing method are disclosed in JP-A-2009-067982.

[0090] The continuous skeleton is composed of a vinyl polymer (such as an aromatic vinyl polymer) containing a crosslinked structural unit in the range of 0.1 to 5.0 mol% among all the constituent units into which an ion exchange group is introduced, and the thickness of the continuous skeleton is three-dimensionally continuous in the range of, for example, 1 to 60 μm, preferably 3 to 58 μm, in the dry state. When the crosslinked structural unit is less than 0.1 mol%, the mechanical strength may be insufficient, and when it exceeds 5.0 mol%, the structure of the porous body may easily deviate from the co-continuous structure. When the thickness of the continuous skeleton is less than 1 μm in the dry state, when the platinum group metal-supported catalyst is filled in the reaction vessel and the reaction liquid is passed through, the monolith ion exchanger may be deformed especially when passing through at a high flow rate. When the thickness of the continuous skeleton exceeds 60 μm in the dry state, the skeleton becomes too thick, and when the platinum group metal-supported catalyst is filled in the reaction vessel and the reaction liquid is passed through, the pressure loss during liquid passage may increase.

[0091] The continuous pores are three-dimensionally continuous between the continuous skeletons in the range of, for example, an average diameter of 10 to 200 μm, preferably 15 to 180 μm, in the dry state. When the average diameter of the continuous pores is less than 10 μm in the dry state, when the platinum group metal-supported catalyst is filled in the reaction vessel and the reaction liquid is passed through, the pressure loss during liquid passage may become large. When the average diameter exceeds 200 μm, when the platinum group metal-supported catalyst is filled in the reaction vessel and the reaction liquid is passed through, the contact between the reaction liquid and the monolith ion exchanger may be insufficient.

[0092] The aforementioned average diameter is measured by the mercury intrusion method and refers to the maximum value of the pore size distribution curve obtained by the mercury intrusion method. The thickness of the continuous skeleton in the dry state is determined by SEM observation of the fourth monolith ion exchanger in the dry state. Specifically, SEM observation of the fourth monolith ion exchanger in the dry state is performed at least three times, the thickness of the skeleton in the obtained images is measured, and their average value is taken as the thickness of the continuous skeleton. Note that the skeleton is rod-shaped and has a circular cross-sectional shape, but those with a different cross-sectional shape such as an elliptical cross-sectional shape may be included. In this case, the thickness is the average of the minor axis and the major axis.

[0093] The total pore volume per unit weight of the fourth monolithic ion exchanger in the dry state is, for example, in the range of 0.5 to 10 mL / g. When the total pore volume is less than 0.5 mL / g, when filling the reaction vessel with the platinum group metal-supported catalyst and passing the reaction liquid through it, the pressure loss during liquid passage may become large. Furthermore, the amount of permeating fluid per unit cross-sectional area may become small, and the processing capacity may decrease. When the total pore volume exceeds 10 mL / g, the mechanical strength decreases, and when filling the reaction vessel with the platinum group metal-supported catalyst and passing the reaction liquid through it, the monolithic ion exchanger may deform especially when passing the liquid at a high flow rate. Furthermore, the contact efficiency between the reaction liquid and the monolithic ion exchanger may decrease.

[0094] The vinyl polymer (aromatic vinyl polymer) constituting the continuous skeleton includes, for example, polystyrene, poly(α-methylstyrene), polyvinylbenzyl chloride, and the like. The above polymers may be polymers obtained by copolymerizing a single vinyl monomer and a crosslinking agent, polymers obtained by polymerizing a plurality of vinyl monomers and a crosslinking agent, or blends of two or more polymers. Among these organic polymer materials, styrene-divinylbenzene copolymers and vinylbenzyl chloride-divinylbenzene copolymers are preferred in terms of ease of forming a co-continuous structure, ease of introducing ion exchange groups, high mechanical strength, and high stability against acids or alkalis.

[0095] The ion exchange capacity per unit weight in the dry state is as described above. Also, "the ion exchange groups are distributed in the organic porous ion exchanger" is as described above.

[0096] (Method for producing the fourth monolithic ion exchanger) The fourth monolithic ion exchanger can be produced, for example, by the following method.

[0097] For example, the fourth monolith can be obtained by performing the following steps I to III after adjusting the water-in-oil emulsion. In step I, for example, the water-in-oil emulsion is polymerized to obtain a monolithic organic porous intermediate (hereinafter referred to as monolith intermediate (4)) having a continuous macroporous structure with a total pore volume of more than, for example, 16 mL / g and 30 mL / g or less. In step II, for example, a mixture containing an aromatic vinyl monomer, an all-oil-soluble monomer having at least two or more vinyl groups in one molecule, a crosslinking agent in the range of, for example, 0.3 to 5 mol%, an organic solvent in which the aromatic vinyl monomer and the crosslinking agent dissolve but the polymer formed by the polymerization of the aromatic vinyl monomer does not dissolve, and a polymerization initiator is prepared. In step III, for example, the mixture obtained in step II is polymerized under standing in the presence of the monolith intermediate (4) obtained in step I to obtain the fourth monolith.

[0098] Step I in the method for producing the fourth monolith is the same as that in the method for producing the first monolith ion exchanger.

[0099] The monolith intermediate (4) obtained in step I is, for example, an organic polymer material having a crosslinked structure, preferably an aromatic vinyl polymer. The crosslinking density of this polymer material includes crosslinked structural units in the range of, for example, 0.1 to 5 mol%, preferably 0.3 to 3 mol% with respect to all the constituent units constituting the polymer material.

[0100] The type of the polymer material of the monolith intermediate (4) is the same as that of the polymer material of the monolith intermediate (3) in the method for producing the third monolith.

[0101] The total pore volume per weight of the monolith intermediate (4) obtained in step I in the dry state is more than, for example, 16 mL / g and 30 mL / g or less, preferably more than 16 mL / g and 25 mL / g or less. As shown in FIG. 7, the monolith intermediate (4) has a skeleton close to a rod shape. When this is made to coexist in the polymerization system, a porous body having a co-continuous structure can be formed using the structure of the monolith intermediate (4) as a mold.

[0102] In the monolithic intermediate (4) obtained in Step I, the average diameter of the openings (mesopores), which are the overlapping parts of macropores, is in the range of, for example, 5 to 100 μm in the dry state.

[0103] Step II in the method for producing the fourth monolith is, for example, a step of preparing a mixture containing an aromatic vinyl monomer, a crosslinking agent in the range of, for example, 0.3 to 5 mol% in all oil-soluble monomers having at least two or more vinyl groups in one molecule, an organic solvent in which the aromatic vinyl monomer and the crosslinking agent dissolve but the polymer produced by the polymerization of the aromatic vinyl monomer does not dissolve, and a polymerization initiator. The order of Step I and Step II may be either one first.

[0104] The aromatic vinyl monomer used in Step II is not particularly limited as long as it contains a polymerizable vinyl group in the molecule and is a lipophilic aromatic vinyl monomer with high solubility in the organic solvent. However, it is preferable to select a vinyl monomer that produces the same type or a similar polymer material as the monolithic intermediate (4) coexisting in the above polymerization system. Specific examples of these vinyl monomers include styrene, α-methylstyrene, vinyltoluene, vinylbenzyl chloride, vinylbiphenyl, vinylnaphthalene, etc. These monomers can be used alone or in combination of two or more. Preferred aromatic vinyl monomers are styrene, vinylbenzyl chloride, etc.

[0105] The addition amount of the aromatic vinyl monomer used in Step II is in the range of, for example, 5 to 50 times, preferably 5 to 40 times, by weight with respect to the monolithic intermediate (4) coexisting during polymerization.

[0106] The crosslinking agent used in the II process preferably contains at least two polymerizable vinyl groups in the molecule and has high solubility in an organic solvent. Examples of the crosslinking agent include divinylbenzene, divinylnaphthalene, divinylbiphenyl, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, butanediol diacrylate, and the like. These crosslinking agents can be used alone or in combination of two or more. The amount of the crosslinking agent used is, for example, in the range of 0.3 to 5 mol%, particularly in the range of 0.3 to 3 mol%, based on the total amount of the vinyl monomer and the crosslinking agent (total oil-soluble monomers). It is preferable that the amount of the crosslinking agent used is substantially equal to the crosslinking density of the monolith intermediate (4) coexisting during the vinyl monomer / crosslinking agent polymerization. If the amounts used of both are too far apart, a deviation in the crosslinking density distribution may occur in the produced monolith, and when introducing an ion exchange group, cracks may easily occur during the ion exchange group introduction reaction.

[0107] The organic solvent used in the II process is, for example, an organic solvent that dissolves aromatic vinyl monomers and crosslinking agents but does not dissolve the polymers produced by the polymerization of aromatic vinyl monomers. In other words, it is a poor solvent for the polymers produced by the polymerization of aromatic vinyl monomers. The organic solvent is, for example, when the aromatic vinyl monomer is styrene, alcohols such as methanol, butanol, and octanol; chain (poly)ethers such as diethyl ether, polyethylene glycol, and polypropylene glycol; chain saturated hydrocarbons such as hexane, heptane, and octane; esters such as ethyl acetate, isopropyl acetate, and ethyl propionate. Also, even if it is a good solvent for polystyrene such as dioxane, THF, or toluene, it can be used as an organic solvent when used together with the above poor solvent and the amount used is small. The amount of these organic solvents used can be such that the concentration of the above aromatic vinyl monomer is, for example, 30 to 80% by weight. If the amount of the organic solvent used deviates from the above range and the concentration of the aromatic vinyl monomer is less than 30% by weight, the polymerization rate may decrease, or the monolith structure after polymerization may deviate from the range of the fourth monolith. On the other hand, if the concentration of the aromatic vinyl monomer exceeds 80% by weight, the polymerization may proceed too far.

[0108] The polymerization initiator used in the II process in the production method of the fourth monolith is the same as the polymerization initiator used in the II process in the production method of the third monolith.

[0109] The III process in the production method of the fourth monolith is, for example, a process in which the mixture obtained in the II process is polymerized under standing in the presence of the monolith intermediate (4) obtained in the I process to change the continuous macroporous structure of the monolith intermediate (4) into a co-continuous structure, and a fourth monolith which is a co-continuous structure monolith is obtained.

[0110] In step III, for example, in a reaction vessel, the monolith intermediate (4) is placed in a state of being impregnated with a mixture (solution). As described above, the mixing ratio of the mixture obtained in step II and the monolith intermediate (4) should be adjusted so that the addition amount of the aromatic vinyl monomer is in the range of, for example, 5 to 50 times by weight, preferably 5 to 40 times by weight, with respect to the monolith intermediate (4). Thereby, a fourth monolith having a co-continuous structure in which pores of an appropriate size are three-dimensionally continuous and a thick skeleton is three-dimensionally continuous can be obtained. In the reaction vessel, the aromatic vinyl monomer and the cross-linking agent in the mixture are adsorbed and distributed on the skeleton of the stationary monolith intermediate (4), and polymerization proceeds within the skeleton of the monolith intermediate (4).

[0111] The polymerization conditions in step III in the method for producing the fourth monolith are the same as the description of the polymerization conditions in step III in the method for producing the third monolith. The fourth monolith ion exchanger can be obtained by performing step IV of introducing an ion exchange group into the fourth monolith obtained in step III. The method for introducing an ion exchange group into the fourth monolith is the same as the method for introducing an ion exchange group into the first monolith.

[0112] (The fifth monolith ion exchanger) The fifth monolith ion exchanger is composed of a continuous skeleton phase and a continuous pore phase. The skeleton has a plurality of protrusions with a size in the range of 4 to 40 μm formed on the surface of the skeleton of a plurality of particulate bodies or organic porous bodies with a diameter in the range of 4 to 40 μm fixed on the surface. The average diameter of the continuous pores is in the range of 10 to 200 μm, the total pore volume is in the range of 0.5 to 10 mL / g, the ion exchange capacity per unit weight in the dry state is in the range of 1 to 9 meq / g, and the ion exchange groups are distributed in the organic porous ion exchanger, which is a monolith ion exchanger.

[0113] The fifth monolithic ion exchanger is a composite structure having an organic porous body with a continuous skeletal phase and a continuous pore phase, and further having a plurality of particulate bodies or a plurality of protrusions, and is a composite structure having a large number of particulate bodies or a large number of protrusions. The fifth monolithic ion exchanger and its manufacturing method are disclosed in JP-A-2009-108294.

[0114] The plurality of particulate bodies are fixed to the skeletal surface of the organic porous body, and their diameter is, for example, in the range of 4 to 40 μm. The plurality of protrusions are formed on the skeletal surface of the organic porous body, and their size is, for example, in the range of 4 to 40 μm in the dry state. The diameter of the particulate body or the size of the protrusion is preferably in the range of 4 to 30 μm, and more preferably in the range of 4 to 20 μm. In the present specification, the "particulate body" and the "protrusion" are collectively referred to as "particulate bodies and the like".

[0115] The average diameter of the continuous pores in the dry state is preferably in the range of 10 to 200 μm.

[0116] The continuous skeletal phase and the continuous pore phase of the fifth monolithic ion exchanger are observed by SEM images. Examples of the basic structure of the fifth monolithic ion exchanger include a continuous macroporous structure and a co-continuous structure. The skeletal phase of the fifth monolithic ion exchanger appears as a columnar continuous body, a continuous body of concave wall surfaces, or a composite thereof, and has a shape clearly different from that of particulate or protrusion shapes.

[0117] The fifth monolithic ion exchanger includes a fifth-1 monolithic ion exchanger or a fifth-2 monolithic ion exchanger. The fifth-1 monolithic ion exchanger is a continuous macroporous structure in which bubble-like macropores overlap, and the overlapping part forms an opening with an average diameter in the range of, for example, 10 to 120 μm in the dry state. The fifth-2 monolithic ion exchanger is a co-continuous structure composed of a three-dimensionally continuous skeleton with a thickness of the continuous skeleton in the dry state in the range of, for example, 0.8 to 40 μm and three-dimensionally continuous pores with an average diameter in the range of, for example, 8 to 80 μm between the skeletons in the dry state. The monoliths before the ion exchange groups are introduced into the fifth-1 and fifth-2 monolithic ion exchangers are called the fifth-1 and fifth-2 monoliths. The average diameter and the thickness of the continuous skeleton in the dry state described above are determined by the same measurement method as that of the fourth monolithic ion exchanger.

[0118] As shown in (A) to (E) in Fig. 8, the protruding portions protruding from the skeleton surface 21 are the protrusions 22a to 22e. As shown in (A), the protrusion 22a has a shape close to a granular shape. As shown in (B), the protrusion 22b is hemispherical. As shown in (C), the protrusion 22c has a shape like a bulge on the skeleton surface. As shown in (D), the length of the protrusion 22d in the plane direction of the skeleton surface 21 is longer than the length in the direction perpendicular to the skeleton surface 21 of the protrusion 22d. As shown in (E), the protrusion 22e has a shape protruding in a plurality of directions. The size of the protrusion is the length of the portion where the width in the SEM image of each individual protrusion is the largest. As shown in Fig. 9, in the fifth monolithic ion exchanger, a plurality of protrusions are formed on the skeleton surface of the organic porous body.

[0119] In the fifth monolithic ion exchanger, in the total particulate matter or the like, the proportion occupied by particulate matter or the like in the range of 4 to 40 μm in the dry state is, for example, 70% or more, preferably 80% or more. The proportion occupied by the aforementioned particulate matter or the like refers to the number ratio of particulate matter or the like of a specific size in the dry state to the number of all particulate matter or the like. Further, the surface of the skeletal phase is coated with, for example, 40% or more, preferably 50% or more, of all particulate matter or the like. Note that the coating ratio of the surface of the skeletal layer by all particulate matter or the like refers to the area ratio on the SEM image when observing the surface by SEM, that is, the area ratio when the surface is viewed in a plan view. If the size of the particles covering the wall surface and the skeleton deviates from the above range, the effect of improving the contact efficiency between the fluid and the skeletal surface and the inside of the monolithic ion exchanger may be liable to be reduced.

[0120] Perform SEM observation of the fifth monolithic ion exchanger in the dry state at least three times. Calculate the diameter or size in the dry state of all particulate matter or the like in the SEM image in the entire field of view, and confirm whether particulate matter or the like with a diameter or size in the range of, for example, 4 to 40 μm is observed. If it is confirmed in the entire field of view, it is determined that particulate matter or the like with a diameter or size in the range of, for example, 4 to 40 μm in the dry state is formed on the skeletal surface of the fifth monolithic ion exchanger. Further, calculate the diameter or size in the dry state of all particulate matter or the like in the SEM image for each field of view according to the above, and for each field of view, obtain the proportion of particulate matter or the like in the range of, for example, 4 to 40 μm in the dry state in all particulate matter or the like. If the proportion of particulate matter or the like in the range of, for example, 4 to 40 μm in the dry state in all particulate matter or the like is 70% or more in the entire field of view, it is determined that the proportion of particulate matter or the like in the range of, for example, 4 to 40 μm in the dry state in all particulate matter or the like formed on the skeletal surface of the fifth monolithic ion exchanger is 70% or more. Further, obtain the coating ratio of the surface of the skeletal layer by all particulate matter or the like in the SEM image for each field of view according to the above. If the coating ratio of the surface of the skeletal layer by all particulate matter or the like is 40% or more in the entire field of view, it is determined that the ratio of the surface of the skeletal layer of the fifth monolithic ion exchanger coated with all particulate matter or the like is 40% or more.

[0121] In the fifth monolithic ion exchanger, if the coverage rate of the surface of the skeletal phase by particulate materials or the like is less than 40%, the effect of improving the contact efficiency between the reaction solution and the inside and surface of the skeleton of the monolithic ion exchanger may be likely to be small. As a method for measuring the coverage rate by the particulate materials or the like, an image analysis method using a SEM image of the fifth monolithic ion exchanger can be mentioned.

[0122] The total pore volume per weight of the fifth monolithic ion exchanger in the dry state is, for example, in the range of 0.5 to 10 mL / g, preferably in the range of 0.8 to 8 mL / g. If the total pore volume is less than 0.5 mL / g, when the platinum group metal-supported catalyst is filled in the reaction vessel and the reaction solution is passed through, the pressure loss during the liquid passage may become large. Furthermore, the amount of permeated fluid per unit cross-sectional area may become small, and the processing capacity may decrease. If the total pore volume exceeds 10 mL / g, the mechanical strength may decrease, and when the platinum group metal-supported catalyst is filled in the reaction vessel and the reaction solution is passed through, the monolithic ion exchanger may be deformed particularly when the liquid is passed through at a high flow rate. Furthermore, the contact efficiency between the reaction solution and the monolithic ion exchanger may decrease.

[0123] In the fifth monolithic ion exchanger, the crosslinking density of the polymer material constituting the skeleton may include crosslinked structural units in the range of, for example, 0.3 to 10 mol%, preferably in the range of 0.3 to 5 mol% with respect to all the constituent units constituting the polymer material. The organic polymer material constituting the skeleton of the fifth monolithic ion exchanger is the same as that of the first monolithic ion exchanger.

[0124] In the fifth monolithic ion exchanger, examples of the material constituting the skeletal phase of the organic porous body and the particulate materials or the like formed on the surface of the skeletal phase include those of the same material with continuous same tissue, and those of different materials with continuous different tissues. Examples of those of different materials with continuous different tissues include cases where the types of vinyl monomers are different from each other, and cases where the types of vinyl monomers and crosslinking agents are the same but the blending ratios are different from each other.

[0125] The fifth monolithic ion exchanger has a thickness of, for example, 1 mm or more and is distinguished from a membrane-like porous body. The thickness of the fifth monolithic ion exchanger is preferably in the range of 3 to 1000 mm.

[0126] The ion exchange capacity per unit weight in the dry state is as described above. Also, the fact that "ion exchange groups are distributed in the organic porous ion exchanger" is as described above.

[0127] (Method for producing the fifth monolithic ion exchanger) The fifth monolithic ion exchanger can be produced, for example, by the following method.

[0128] The fifth monolith can be obtained, for example, by preparing a water-in-oil emulsion and then performing the following steps I to III. In step I, for example, the water-in-oil emulsion is polymerized to obtain a monolithic organic porous intermediate (hereinafter referred to as monolith intermediate (5)) having a continuous macroporous structure with a total pore volume in the range of, for example, 5 to 30 mL / g. In step II, for example, a mixture containing a vinyl monomer, a crosslinking agent having at least two or more vinyl groups in one molecule, an organic solvent in which the vinyl monomer and the crosslinking agent dissolve but the polymer produced by the polymerization of the vinyl monomer does not dissolve, and a polymerization initiator is prepared. In step III, for example, the mixture obtained in step II is polymerized under standing in the presence of the monolith intermediate (5) obtained in step I to obtain the fifth monolith.

[0129] Step I in the method for producing the fifth monolith is the same as step I in the method for producing the third monolith.

[0130] In Step I, when forming an oil-in-water droplet type emulsion, a polymerization initiator may be used as necessary. As the polymerization initiator, a compound that generates radicals by heat or light irradiation is preferably used. The polymerization initiator may be water-soluble or oil-soluble. Examples thereof include 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), dimethyl 2,2'-azobisisobutyrate, 4,4'-azobis(4-cyanovaleric acid), 1,1'-azobis(cyclohexane-1-carbonitrile), benzoyl peroxide, lauroyl peroxide, potassium persulfate, ammonium persulfate, hydrogen peroxide-ferrous chloride, sodium persulfate-sodium acid sulfite, and the like.

[0131] The monolith intermediate (5) obtained in Step I has a continuous macroporous structure. When this is allowed to coexist in the polymerization system, a particulate body or the like is formed on the surface of the skeletal phase of the continuous macroporous structure using the structure of the monolith intermediate (5) as a template, or a particulate body or the like is formed on the surface of the skeletal phase of the co-continuous structure. Further, the monolith intermediate (5) is an organic polymer material having a crosslinked structure. The crosslinking density of the polymer material contains crosslinked structural units in the range of, for example, 0.3 to 10 mol%, preferably 0.3 to 5 mol% with respect to all the constituent units constituting the polymer material.

[0132] The type of the polymer material of the monolith intermediate (5) is the same as the type of the polymer material of the monolith intermediate (3) in the method for producing the third monolith.

[0133] The total pore volume per unit weight of the monolith intermediate (5) obtained in Step I in the dry state is, for example, in the range of 5 to 30 mL / g, preferably in the range of 6 to 28 mL / g. In order to make the total pore volume of the monolith intermediate (5) within the above numerical range, the ratio (by weight) of the monomer to water may be, for example, approximately 1:5 to 1:35.

[0134] In Step I, if the ratio of this monomer to water is approximately 1:5 to 1:20, a monolith intermediate (5) with a continuous macropore structure having a total pore volume of, for example, 5 to 16 mL / g can be obtained, and the monolith obtained through Step III becomes the Monolith No. 5-1. On the other hand, if the ratio of the monomer to water is approximately 1:20 to 1:35, a monolith intermediate (5) with a continuous macropore structure having a total pore volume exceeding, for example, 16 mL / g and not exceeding 30 mL / g can be obtained, and the monolith obtained through Step III becomes the Monolith No. 5-2.

[0135] The monolith intermediate (5) obtained in Step I in the method for producing the fifth monolith has an average diameter in the dry state of the openings (mesopores), which are the overlapping parts of the macropores, of, for example, 20 to 200 μm.

[0136] Step II in the method for producing the fifth monolith is the same as Step II in the method for producing the third monolith. In Step III in the method for producing the fifth monolith, for example, the mixture obtained in Step II is polymerized while standing and in the presence of the monolith intermediate (5) obtained in Step I to obtain the fifth monolith.

[0137] Here, as disclosed in Japanese Patent Publication No. 7-501140 and the like, when a vinyl monomer and a crosslinking agent are subjected to bulk polymerization in a specific organic solvent in the absence of the monolith intermediate (5), a particulate-aggregation-type monolithic organic porous body can be obtained. In contrast, when the monolith intermediate (5) having a continuous macropore structure is present in the above polymerization system, the structure of the composite monolith after polymerization changes dramatically, and the fifth monolith having the above-described specific skeletal structure can be obtained instead of the particulate-aggregation structure.

[0138] In the III process of the method for manufacturing the fifth monolith, the internal volume of the reaction vessel is not particularly limited as long as it is large enough to accommodate the monolith intermediate (5) in the reaction vessel. When the monolith intermediate (5) is placed in the reaction vessel, it may be either a type that allows a gap to form around the monolith in plan view or a type that allows the monolith intermediate (5) to fit into the reaction vessel with almost no gap. Among these, the type in which the fifth monolith after polymerization hardly receives pressure from the inner wall of the container and fits into the reaction vessel with almost no gap is efficient with almost no waste of reaction raw materials, etc., and hardly causes distortion in the fifth monolith. Even when the internal volume of the reaction vessel is large and there is a gap around the fifth monolith after polymerization, since the vinyl monomer and the crosslinking agent are adsorbed and distributed on the monolith intermediate (5), hardly any particle aggregation structure is generated in the gap portion in the reaction vessel.

[0139] In this III process, for example, in the reaction vessel, the monolith intermediate (5) is placed in a state of being impregnated with a mixture (solution). As described above, the mixing ratio of the mixture obtained in the II process and the monolith intermediate (5) may be adjusted so that the addition amount of the vinyl monomer is in the range of, for example, 3 to 50 times, preferably 4 to 40 times, by weight with respect to the monolith intermediate (5). Thereby, it is possible to obtain the fifth monolith, which is a composite monolith having a specific skeleton while having an appropriate pore diameter. In the reaction vessel, the vinyl monomer and the crosslinking agent in the mixture are adsorbed and distributed on the skeleton of the stationary monolith intermediate (5), and polymerization proceeds within the skeleton of the monolith intermediate (5).

[0140] In the III process of the method for manufacturing the fifth monolith, the polymerization conditions are almost the same as those in the III process of the method for manufacturing the third monolith.

[0141] When manufacturing the above-mentioned fifth monolith, when performing the II process or the III process under at least one of the conditions (1) to (x) below, it is possible to manufacture a monolith having a particle body or the like formed on the skeleton surface. (1) The polymerization temperature in the III process is at least 5 °C lower than the 10-hour half-life temperature of the polymerization initiator. (2) The molar percentage of the crosslinking agent used in the II process is 2 times or more the molar percentage of the crosslinking agent used in the I process. (3) The vinyl monomer used in the II process is a vinyl monomer having a structure different from the oil-soluble monomer used in the I process. (4) The organic solvent used in the II process is a polyether having a molecular weight of 200 or more. (5) The concentration of the vinyl monomer used in the II process is 30% by weight or less in the mixture of the II process.

[0142] Preferred structures of the fifth monolith thus obtained include a continuous macroporous structure (the "fifth-1 monolith") in which bubble-like macropores overlap and the overlapping portions become openings in the range of, for example, an average diameter of 10 to 120 μm in the dry state, and a co-continuous structure (the "fifth-2 monolith") composed of a three-dimensionally continuous skeleton with a thickness of the continuous skeleton in the dry state in the range of, for example, 0.8 to 40 μm and three-dimensionally continuous pores with a diameter in the range of, for example, 8 to 80 μm between the skeletons. Note that the method for introducing an ion exchange group into the fifth monolith is the same as the method for introducing an ion exchange group into the first monolith.

[0143] [Platinum group metal-supported catalyst] The platinum group metal-supported catalyst used in the catalytic hydrogenation reduction method according to this embodiment is a catalyst in which at least one of platinum group metal ions, platinum group metal complex ions, and platinum group metal nanoparticles with an average particle diameter in the range of 1 to 100 nm is supported on the above non-particulate weakly basic organic porous ion exchanger, for example, any one of the first to fifth monolithic ion exchangers. That is, in the platinum group metal-supported catalyst, the platinum group metal is supported on the above non-particulate weakly basic organic porous ion exchanger in the state of nanoparticles or ions. For example, the platinum group metal-supported catalyst is a catalyst in which platinum group metal ions or platinum group metal complex ions are bonded by ionic bonds or coordination bonds to the weak anion exchange groups in the above ion exchanger, such as tertiary amino groups like dimethylamino groups and diethylamino groups.

[0144] The platinum group metals are ruthenium, rhodium, palladium, osmium, iridium, and platinum. These platinum group metals may be a single type alone, a combination of two or more metals, or two or more metals may be used as an alloy. Among these, platinum, palladium, and platinum / palladium alloys are preferable in terms of high catalytic activity.

[0145] The average particle diameter of the platinum group metal nanoparticles is in the range of 1 to 100 nm, preferably in the range of 1 to 50 nm, and more preferably in the range of 1 to 20 nm. If the average particle diameter of the platinum group metal nanoparticles is less than 1 nm, the platinum group metal particles may desorb from the carrier. If it exceeds 100 nm, the surface area per unit mass of the metal may decrease and the catalytic effect may not be obtained efficiently.

[0146] The average particle diameter of the platinum group metal nanoparticles is determined by image analysis of the TEM images obtained by transmission electron microscope (TEM) analysis. Specifically, first, the surface of the platinum group metal-supported catalyst is analyzed by TEM. Next, in the obtained TEM image, a field of view with 200 or more particles is arbitrarily selected, and the TEM image of that field of view is analyzed by image analysis to measure the particle diameters of all the particles in the field of view. If the number of platinum group metal particles supported in one field of view is less than 200, two or more fields of view are arbitrarily selected, and the particle diameters are measured for all the particles in the two or more selected fields of view. Next, the average particle diameter of the platinum group metal nanoparticles is calculated using the formula "Average particle diameter of platinum group metal particles (nm) = Total particle diameter of all measured particles (nm) / Number of measured particles (pieces)".

[0147] The platinum group metal ions are the ions of the above platinum group metals, and the valence of the platinum group metal ions varies depending on the type of platinum group metal. These platinum group metal ions may be a single type or a combination of two or more metals. Among these, platinum ions and palladium ions are preferable in terms of high catalytic activity.

[0148] The platinum group metal complex ions are the complex ions of the above platinum group metals and are not particularly limited as long as they are platinum group metal complex ions. Specific examples of platinum group metal compounds include, for example, tetrachloropalladate ion, tetraamminepalladium ion, hexachloropalladate ion, tetrachloroplatinate ion, hexachloroplatinate ion, tetraammineplatinum ion, hexaammineplatinum ion, tetranitroplatinate ion, hexahydroxyplatinate ion, hexaammine rhodium ion, hexachloroiridium ion, hexaammineiridium ion, hexachlororuthenium ion, hexaammine ruthenium ion, hexaammineosmium ion, etc. These platinum group metal complex ions may be a single type or a combination of two or more metals. Among these, platinum complex ions and palladium complex ions are preferable in terms of high catalytic activity.

[0149] In the noble metal-supported catalyst, the fact that noble metals and the like are supported can be confirmed by performing transmission electron microscope (TEM) observation.

[0150] The supported amount of noble metals and the like in the noble metal-supported catalyst ((weight in terms of noble metal atoms / weight of the noble metal-supported catalyst in the dry state) × 100) is in the range of 0.01 to 10% by weight in the dry state, preferably in the range of 0.1 to 5.0% by weight. When the supported amount of noble metals and the like is less than 0.01% by weight in the dry state, the catalytic activity may be insufficient, and when it exceeds 10% by weight, metal elution into water may be observed. The quantification of noble metal atoms in the noble metal-supported catalyst is performed using an ICP emission spectrometer.

[0151] There is no particular limitation on the method for producing the noble metal-supported catalyst, and a noble metal-supported catalyst can be obtained by supporting noble metals and the like on the above-mentioned monolithic ion exchanger by a known method. For example, a method in which a monolithic ion exchanger in the dry state is immersed in an organic solution of a noble metal compound at a predetermined temperature for a predetermined time to adsorb noble metal ions onto the monolithic ion exchanger by ion exchange, or a method in which the monolithic ion exchanger is immersed in an aqueous solution of a noble metal complex compound such as tetraamminepalladium complex at a predetermined temperature for a predetermined time, and the noble metal ions are adsorbed and supported on the monolithic ion exchanger by ion exchange, etc. can be mentioned.

[0152] The loading of noble metals and the like onto the monolithic ion exchanger may be either batchwise or continuous, and there is no particular limitation.

[0153] As the platinum group metal compound used in the method for producing a platinum group metal-supported catalyst, either an organic salt or an inorganic salt may be used, and examples thereof include halides, sulfates, nitrates, phosphates, organic acid salts, inorganic complex salts, and the like. Specific examples of the platinum group metal compound include palladium chloride, palladium nitrate, palladium sulfate, palladium acetate, tetraamminepalladium chloride, tetraamminepalladium nitrate, platinum chloride, tetraammineplatinum chloride, tetraammineplatinum nitrate, chlorotriammineplatinum chloride, hexaammineplatinum chloride, hexaammineplatinum sulfate, chloropentammineplatinum chloride, cis-tetrachlorodiammineplatinum chloride, trans-tetrachlorodiammineplatinum chloride, rhodium chloride, rhodium acetate, hexaammine rhodium chloride, hexaammine rhodium bromide, hexaammine rhodium sulfate, pentaammineaquarhodium chloride, pentaammineaquarhodium nitrate, cis-dichlorotetraammine rhodium chloride, trans-dichlorotetraammine rhodium chloride, ruthenium chloride, hexaammine ruthenium chloride, hexaammine ruthenium bromide, hexaammine ruthenium iodide, chloropentammine ruthenium chloride, cis-dichlorotetraammine ruthenium chloride, trans-dichlorotetraammine rhodium chloride, iridium(III) chloride, iridium(IV) chloride, hexaammine iridium chloride, hexaammine iridium nitrate, chloropentammine iridium chloride, chloropentammine iridium bromide, hexaammine osmium chloride, hexaammine osmium bromide, hexaammine osmium iodide, and the like. The usage amount of these compounds is, for example, 0.005 to 30% by weight in terms of metal relative to the monolith ion exchanger as the carrier.

[0154] When supporting platinum group metals or the like, platinum group metal compounds are usually dissolved in a solvent and used. As the solvent, water; alcohols such as methanol, ethanol, propanol, butanol, and benzyl alcohol; ketones such as acetone and methyl ethyl ketone; nitriles such as acetonitrile; amides such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone, and mixtures thereof are used. Further, in order to enhance the solubility of the platinum group metal compound in the solvent, acids such as hydrochloric acid, sulfuric acid, and nitric acid, and bases such as sodium hydroxide and tetramethylammonium hydroxide may be added.

[0155] There is no particular limitation on the reducing agent used in the method for producing a platinum group metal-supported catalyst, and reducing gases such as hydrogen and ethylene; alcohols such as methanol, ethanol, propanol, butanol, and benzyl alcohol; carboxylic acids such as formic acid, ammonium formate, oxalic acid, citric acid, sodium citrate, ascorbic acid, and calcium ascorbate and salts thereof; aldehydes such as formaldehyde and acetaldehyde; hydrazines such as hydrazine, methylhydrazine, ethylhydrazine, butylhydrazine, allylhydrazine, and phenylhydrazine; hypophosphites such as Acid sodium hypophosphite and potassium hypophosphite; sodium borohydride and the like can be mentioned.

[0156] There are also no particular restrictions on the reaction conditions of the reduction reaction. For example, the reaction is carried out at a temperature of -20°C to 150°C for 1 minute to 24 hours to reduce the platinum group metal compound to a zero-valent platinum group metal.

[0157] [Contact hydrogenation reduction method] The contact hydrogenation reduction method according to this embodiment is a method for performing contact hydrogenation reduction of a reaction substrate by bringing the reaction substrate into contact with a hydrogen source in the presence of the above platinum group metal-supported catalyst.

[0158] Examples of the hydrogen source include reducing gases such as hydrogen; alcohols such as methanol, ethanol, and propanol; hydrazine and its derivatives such as hydrazine, methylhydrazine, allylhydrazine, and phenylhydrazine, and their salts; formic acid and its salts; hypophosphorous acid and its salts, etc. Among these hydrogen sources, hydrogen and hydrazine are preferably used.

[0159] The usage amount of the hydrogen source may be, for example, in the range of 1 to 100 times the molar amount relative to the reaction substrate.

[0160] There is no particular limitation on the method for introducing the hydrogen source into the reaction system. For example, when the hydrogen source is hydrogen, hydrogen may be introduced into the reaction system under normal pressure or under pressure. Also, when the hydrogen source is hydrazine, it may be introduced into the reaction system as an aqueous solution.

[0161] The reaction substrate is a compound having a functional group or site to be hydrogenated, and there is no particular limitation. For example, it includes compounds having unsaturated bonds such as carbon-carbon double bonds and carbon-carbon triple bonds, compounds having nitro groups such as aromatic nitro compounds, compounds having ester groups such as aromatic benzyl esters, compounds having carbonyl groups, etc. More specific reaction substrates include aromatic nitro compounds, aromatic benzyl ester compounds, aromatic benzyl ether compounds, aromatic halides, compounds having an N-benzyloxycarbonyl group, alkynes, alkenes, etc. These compounds are converted into aromatic amino compounds, compounds having a carboxyl group, compounds having a hydroxyl group, aromatic hydrocarbon compounds, compounds having an amino group, alkanes, etc. respectively by catalytic hydrogenation reduction reaction.

[0162] The usage amount of the platinum group metal-supported catalyst is, for example, in the range of 0.000001 to 1 mole in terms of the platinum group metal supported per 1 mole of the reaction substrate.

[0163] In the catalytic hydrogenation reduction method according to this embodiment, in addition to the reaction substrate, the above-mentioned platinum group metal-supported catalyst, and the hydrogen source, a solvent may be used. Specific examples of the solvent include water; alcohols such as methanol, ethanol, propanol, and butanol; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; nitriles such as acetonitrile and butyronitrile; halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, and dichloroethane; ethers such as diethyl ether, dimethoxymethane, dimethoxyethane, and tetrahydrofuran; aliphatic hydrocarbons such as hexane, cyclohexane, heptane, and octane; aromatic hydrocarbons such as benzene, toluene, xylene, and naphthalene; esters such as ethyl acetate and butyl acetate. These solvents may be used alone or in combination of two or more. Also, by selecting the solvent to be used and its combination, it is possible to control the selectivity of the catalytic hydrogenation reduction reaction.

[0164] The reaction conditions in the catalytic hydrogenation reduction method according to this embodiment are not particularly limited, but the reaction temperature is, for example, in the range of -20°C to 200°C, preferably in the range of 10 to 100°C. Also, the reaction time is, for example, in the range of 1 minute to 48 hours, preferably in the range of 5 minutes to 24 hours. The reaction pressure is, for example, in the range of normal pressure to 10 MPa, preferably in the range of normal pressure to 5 MPa.

[0165] Examples of the hydrogenation reduction reaction include reduction of a nitro group to an amino group, reduction of an azide group to an amino group, reduction of a carbon-carbon double bond, reduction of a carbon-carbon triple bond, elimination of a protecting group for a hydroxyl group or a carboxyl group such as a benzyl protecting group, elimination of a protecting group for an amino group such as a benzyloxycarbonyl group (Cbz group), reduction of an epoxide to an alcohol, reduction of an aromatic ketone to an alcohol and a deoxygenation reaction, etc.

[0166] As a preferred embodiment of the catalytic hydrogenation reduction method, for example, a cylindrical reaction vessel filled with the above-mentioned platinum group metal-supported catalyst is continuously supplied with a reaction substrate and a hydrogen source, and in the presence of the platinum group metal-supported catalyst, the reaction substrate and the hydrogen source are continuously brought into contact to perform catalytic hydrogenation reduction of the reaction substrate. Examples include a fixed-bed continuous flow-type catalytic hydrogenation reduction method and the like.

[0167] An example of the configuration of a reaction apparatus for performing such a fixed-bed continuous flow-type catalytic hydrogenation reduction method is shown in FIG. 17.

[0168] The catalytic hydrogenation reduction apparatus 50 shown in FIG. 17 includes, for example, a cylindrical reaction vessel 52 filled with the above-mentioned platinum group metal-supported catalyst, a reaction substrate vessel 54 for containing the reaction substrate, a reaction substrate supply pump 58 for supplying the reaction substrate to the reaction vessel 52, a mixer 60 as a mixing means for mixing a hydrogen source into the reaction substrate, a reaction liquid receiver 56 for containing the reaction liquid discharged from the reaction vessel 52, a reaction substrate supply pipe 66 connecting the reaction substrate vessel 54 and the reaction vessel 52, with the reaction substrate supply pump 58 and the mixer 60 installed therein, a hydrogen source supply pipe 64 connected to the mixer 60, a reaction liquid discharge pipe 68 connecting the reaction vessel 52 and the reaction liquid receiver 56, with a switching valve 62 attached thereto, and a circulation pipe 70 branched from the reaction liquid discharge pipe 68 by the switching valve 62 and connected to the reaction substrate vessel 54. Further, a heating means for heating the inside of the reaction vessel 52 may be attached to the reaction vessel 52 as necessary.

[0169] In the catalytic hydrogenation reduction apparatus 50, the reaction substrate is continuously supplied from the reaction substrate container 54 to the reaction vessel 52 by the reaction substrate supply pump 58. At this time, in the mixer 60 installed in the middle of the reaction substrate supply pipe 66, the hydrogen source continuously supplied from the hydrogen source supply pipe 64 is mixed with the reaction substrate. Then, the reaction raw material, which is a mixture of the reaction substrate and the hydrogen source, is supplied to the reaction vessel 52. The reaction raw material supplied into the reaction vessel 52 passes through the continuous pores of the platinum group metal-supported catalyst filled in the reaction vessel 52, specifically, through the continuous pores of the non-particulate weakly basic organic porous ion exchanger. As a result, in the presence of the platinum group metal-supported catalyst, the reaction substrate and the hydrogen source are continuously brought into contact, and the catalytic hydrogenation reduction of the reaction substrate is carried out. Next, the reaction solution after the catalytic hydrogenation reduction is sent to the reaction solution receiver 56 through the reaction solution discharge pipe 68. The reaction solution after the catalytic hydrogenation reduction may be returned to the reaction substrate container 54 through the circulation pipe 70 branched from the reaction solution discharge pipe 68. Note that the switching between the feeding of the reaction solution to the reaction solution receiver 56 and the return to the reaction substrate container 54 is performed by the switching valve 62. By switching between the feeding of the reaction solution to the reaction solution receiver 56 and the return to the reaction substrate container 54, it is possible to pass the solution through the layer of the platinum group metal-supported catalyst in the reaction vessel 52 only once for reaction, or to pass the solution through the layer of the platinum group metal-supported catalyst two or more times for reaction.

[0170] The reaction conditions in the fixed-bed continuous flow catalytic hydrogenation reduction method are not particularly limited. For example, the reaction temperature is in the range of -20°C to 200°C, preferably in the range of 10 to 100°C. The reaction pressure is, for example, in the range of normal pressure to 10 MPa, preferably in the range of normal pressure to 5 MPa.

[0171] Since the platinum group metal-supported catalyst has a high contact efficiency with the reaction substrate and the hydrogen source, which are the reaction raw materials, when performing the catalytic hydrogenation reduction reaction in a fixed-bed continuous flow manner, the reaction can be sufficiently carried out even if the liquid passing rate is increased. Therefore, the space velocity (SV) can be increased. The space velocity (SV) is, for example, in the range of 0.1 to 10000 h -1 preferably in the range of 1 to 1000 h -1 is the range.

[0172] In the catalytic hydrogenation reduction apparatus 50, the size of the reaction vessel 52, the thickness of the packed bed of the platinum group metal-supported catalyst, the flow rate of the reaction substrate, the flow rate of the hydrogen source, the pressure of the hydrogen source, the flow direction (upward, downward, or lateral) of the reaction substrate and the hydrogen source, etc. may be appropriately selected according to the type of reaction, reaction conditions, etc.

[0173] The platinum group metal-supported catalyst used in the catalytic hydrogenation reduction method according to this embodiment has a higher reaction rate and higher catalytic activity than conventional platinum group metal-supported catalysts. Also, in a homogeneous organic reaction in which the catalyst is dissolved in the reaction solvent, in order to make the reaction field basic, the reaction solvent must be made basic. In contrast, when the above platinum group metal-supported catalyst is used, the reaction solvent can remain neutral and the inside of the carrier serving as the reaction field can be made basic.

Examples

[0174] Hereinafter, examples and comparative examples will be given to describe the present invention more specifically and in detail, but the present invention is not limited to the following examples.

[0175] [Production of weakly basic monolith anion exchanger] According to the production method of the fifth monolith ion exchanger, a monolith was produced, and an ion exchange group was introduced into the obtained monolith.

[0176] (Production of monolith intermediate (Step I)) 9.28 g of styrene, 0.19 g of divinylbenzene as monomers, 0.50 g of sorbitan monooleate (hereinafter abbreviated as SMO) as a surfactant, and 0.25 g of 2,2'-azobis(isobutyronitrile) as a polymerization initiator were mixed and dissolved uniformly. Next, this styrene / divinylbenzene / SMO / 2,2'-azobis(isobutyronitrile) mixture was added to 180 g of pure water, and stirred under reduced pressure using a vacuum stirring and defoaming mixer (manufactured by EMI Co., Ltd.), a planetary stirring device, to obtain a water-in-oil droplet type emulsion. This emulsion was quickly transferred to a reaction vessel, sealed, and polymerized at 60 °C for 24 hours under standing. After the polymerization was completed, the content was taken out, extracted with methanol, and then dried under reduced pressure to produce a monolith intermediate having a continuous macroporous structure. The internal structure of the thus obtained monolith intermediate (dry body) was observed by SEM. The SEM image is shown in Fig. 10. Although the wall portion partitioning two adjacent macropores is extremely thin and rod-shaped, it has a continuous macroporous structure. The average diameter of the openings (mesopores) of the portions where the macropores overlap with the macropores measured by mercury intrusion porosimetry was 40 μm, and the total pore volume was 18.2 mL / g.

[0177] (Production of Monolith (II Process)) Next, 216.6 g of styrene as a monomer, 4.4 g of divinylbenzene as a crosslinking agent, 220 g of 1-decanol as an organic solvent, and 0.8 g of 2,2'-azobis(2,4-dimethylvaleronitrile) as a polymerization initiator were mixed and dissolved uniformly (II Process).

[0178] (Production of Monolith (III Process)) Next, the above monolith intermediate was placed in a reaction vessel, immersed in this styrene / divinylbenzene / 1-decanol / 2,2'-azobis(2,4-dimethylvaleronitrile) mixture, defoamed in a reduced pressure chamber, and then the reaction vessel was sealed and polymerized at 50 °C for 24 hours under standing. After the polymerization was completed, the content was taken out, Soxhlet extracted with acetone, and then dried under reduced pressure (III Process).

[0179] The results of observing the internal structure of a monolith (dry body) containing 1.2 mol% of a crosslinked component composed of the styrene / divinylbenzene copolymer thus obtained by SEM are shown in Fig. 11. As is clear from Fig. 11, this monolith had a continuous skeletal phase and a continuous pore phase in which the skeleton and pores were three-dimensionally continuous, respectively, and the two phases were intertwined in a co-continuous structure. Also, the thickness of the skeleton measured from the SEM image was 20 μm. Further, the average diameter of the three-dimensionally continuous pores of this monolith measured by mercury intrusion porosimetry was 70 μm, and the total pore volume was 4.4 mL / g. The average pore diameter was determined from the maximum value of the pore size distribution curve obtained by mercury intrusion porosimetry.

[0180] (Production of chloromethylated monolith) The produced monolith was placed in a column reactor, and a solution containing 1600 g of chlorosulfonic acid, 400 g of tin tetrachloride, and 2500 mL of dimethoxymethane was circulated and passed through for reaction at 30 °C for 5 hours to introduce chloromethyl groups. After completion of the reaction, the chloromethylated monolith was washed with a mixed solvent of THF / water = 2 / 1 (vol), and further washed with THF to obtain a chloromethylated monolith.

[0181] (Production of weakly basic monolith anion exchanger) Next, the chloromethylated monolith was dried under reduced pressure. The weight of the dried chloromethylated monolith was 8.4 g. This chloromethylated monolith was placed in a separable flask containing a stir bar, and a solution containing 56 mL of a 50% aqueous solution of dimethylamine as a secondary amine and 180 mL of THF was introduced into the separable flask and stirred under reflux for 10 hours. After completion of the reaction, the product was washed with methanol and then with pure water to obtain a weakly basic monolith anion exchanger.

[0182] The total anion exchange capacity of the obtained weakly basic monolith anion exchanger in the dry state was 4.7 meq / g, and the weak anion exchange capacity was 4.3 meq / g. Also, the thickness of the continuous skeleton in the dry state measured from the SEM image was 25 μm.

[0183] (Production of Platinum Group Metal-Supported Catalyst (Weakly Basic Monolithic Anion Exchanger Supported with Pd Ions)) The weakly basic monolithic anion exchanger was dried under reduced pressure. The weight of the dried weakly basic monolithic anion exchanger was 8.7 g. This dried monolith was treated with hydrochloric acid in methanol and then immersed in dilute hydrochloric acid in which 146 mg of palladium chloride was dissolved for 24 hours to attach tetrachloropalladate ions. After the immersion, it was washed several times with pure water to prepare a Pd ion-supported weakly basic monolithic anion exchanger. When the palladium loading amount in the obtained Pd ion-supported weakly basic monolithic anion exchanger was determined using an ICP emission spectrometer (PS3520UVDDII, manufactured by Hitachi High-Technologies Corporation), the palladium loading amount was 1.0 wt%. Also, the analysis results of EPMA (Electron Probe Micro Analyzer) and ESCA (Electron Spectroscopy for Chemical Analysis) of the obtained Pd ion-supported weakly basic monolithic anion exchanger are shown in FIGS. 12 and 13, respectively.

[0184] (Production of Platinum Group Metal-Supported Catalyst (Weakly Basic Monolithic Anion Exchanger Supported with Pd Nanoparticles)) The produced Pd ion-supported weakly basic monolithic anion exchanger was filled into a column (size of the cut-out catalyst: diameter 4.6 mm × length 30 mm (when immersed in water)). The temperature of the column was 80°C, pressurized to 0.3 MPa with a back pressure valve, and hydrogen gas was supplied at a flow rate of 25 mL / min and toluene at 0.5 mL / min to reduce Pd ions. After the obtained Pd nanoparticle-supported weakly basic monolithic anion exchanger was dried under reduced pressure, Pd particle size analysis was performed by TEM analysis. The TEM analysis results are shown in FIG. 14.

[0185] (Production of Platinum Group Metal-Supported Catalyst (Weakly Basic Monolithic Anion Exchanger Supported with Pt Ions)) The manufactured weakly basic monolithic anion exchanger was dried under reduced pressure. The weight of the dried weakly basic monolithic anion exchanger was 6.7 g. This dried weakly basic monolithic anion exchanger was placed in a separable flask containing a stir bar, immersed in a 1 N hydrochloric acid / methanol solution, and stirred at room temperature (25 ± 2°C) for 1 day. Then, the hydrochloric acid-treated weakly basic monolithic anion exchanger was immersed in 150 mL of a 0.142 g potassium chloroplatinate (II) solution and stirred at room temperature (25 ± 2°C) for 1 day to support platinum ions on the weakly basic monolithic anion exchanger. The obtained Pt ion-supported weakly basic monolithic anion exchanger was washed several times with pure water and then dried by reduced pressure drying. When the supported amount of palladium in the Pt ion-supported weakly basic monolithic anion exchanger was determined using an ICP emission spectroscopic analyzer (PS3520UVDDII manufactured by Hitachi High-Technologies Science), the platinum supported amount was 0.57 wt%. Also, the distribution state of platinum was observed by EPMA (Electron Probe Micro Analyzer). The distribution state of platinum in the skeletal cross-section of the Pt ion-supported weakly basic monolithic anion exchanger is shown in Fig. 15. It was confirmed that platinum was distributed not only on the skeletal surface of the weakly basic monolithic anion exchanger but also inside the skeleton, and although the concentration was slightly higher inside, it was distributed relatively uniformly.

[0186] (Production of Powdered Palladium-Supported Catalyst) The prepared platinum group metal-supported catalyst (Pd nanoparticle-supported weakly basic monolithic anion exchanger) was pulverized using a mortar to produce a powdered 1.0 wt% Pd-supported catalyst.

[0187] (Production of Pd Nanoparticle-Supported Strongly Basic Monolithic Anion Exchanger) The Pd nanoparticle-supported strongly basic monolithic anion exchanger was produced based on Japanese Patent Application Laid-Open No. 2014-030821.

[0188] (Production of Pd Nanoparticle-Supported Strongly Acidic Monolithic Cation Exchanger) The Pd nanoparticle-supported strongly acidic monolithic cation exchanger was produced based on Japanese Patent Application Laid-Open No. 2014-030821.

[0189] [Contact hydrogenation reduction by continuous flow (circulation method)] (Example 1-1: Hydrogenation reduction reaction of diphenylacetylene) A Pd ion-supported weakly basic monolith anion exchanger with a palladium loading of 1.0 wt% was packed into a cylindrical column made of resin (size of the cut-out catalyst: diameter 4.6 mm × length 30 mm (when immersed in water)). Next, a substrate solution was prepared by dissolving 6.0 mmol of diphenylacetylene in 20 mL of ethanol. The temperature of the column was set to 80 °C, pressurized to 0.3 MPa with a back pressure valve, and supplied at a substrate solution flow rate of 0.5 mL / min and a hydrogen gas flow rate of 10 mL / min to conduct the hydrogenation reduction reaction. At this time, the SV of the substrate solution was 60 h -1 It was. Also, the total contact time between the substrate solution and the catalyst layer was 1 minute. The reaction product was 1,2-diphenylethane. When the conversion rate to 1,2-diphenylethane after 3 h of the reaction was calculated by GC (GC-2010Plus manufactured by Shimadzu Corporation), it was 94%. For subsequent examples and comparative examples, the conversion rate was also calculated by GC analysis

[0190] (Example 1-2: Hydrogenation reduction reaction of diphenylacetylene) The same method as in Example 1-1 was carried out except that the column temperature was changed from 80 °C to 60 °C and the pressure was changed from 0.3 MPa to atmospheric pressure. The reaction product was 1,2-diphenylethane, and the conversion rate to 1,2-diphenylethane after 3 h of the reaction was 95%

[0191] (Comparative Example 1-1: Hydrogenation reduction reaction of diphenylacetylene) The same method as in Example 1-1 was carried out except that the catalyst used was changed from a Pd ion-supported weakly basic monolith anion exchanger with a palladium loading of 1.0 wt% to a Pd ion-supported strongly basic monolith anion exchanger with a palladium loading of 1.0 wt%. The reaction product was 1,2-diphenylethane, and the conversion rate was 70%

[0192] (Example 1-3: Hydrogenation reduction reaction of 2-nitrobiphenyl) A Pd ion-supported weakly basic monolithic anion exchanger with a palladium loading of 1.0 wt% was packed into a resin cylindrical column (the size of the cut-out catalyst: diameter 4.6 mm × length 30 mm (when immersed in water)). Next, a substrate solution was prepared by dissolving 6.0 mmol of 2-nitrobiphenyl in 20 mL of ethanol. The temperature of the column was set at 80 °C and pressurized to 0.3 MPa with a back pressure valve. The substrate solution was supplied at a flow rate of 0.5 mL / min and hydrogen gas at a flow rate of 10 mL / min to conduct a hydrogenation reduction reaction. At this time, the space velocity (SV) of the substrate solution was 60 h -1 The total contact time between the substrate solution and the catalyst layer was 1 minute. The reaction product was 2-aminobiphenyl, and the conversion rate to 2-aminobiphenyl after 3 hours of reaction was 56%.

[0193] (Example 1-4: Hydrogenation reduction reaction of 2-nitrobiphenyl) The reaction was carried out in the same manner as in Examples 1-3, except that the column temperature was changed from 80 °C to 60 °C and the pressure was changed from 0.3 MPa to atmospheric pressure. The reaction product was 2-aminobiphenyl, and the conversion rate was 45%.

[0194] (Comparative Example 1-2: Hydrogenation reduction reaction of 2-nitrobiphenyl) The reaction was carried out in the same manner as in Examples 1-3, except that the catalyst used was changed from a Pd ion-supported weakly basic monolithic anion exchanger with a palladium loading of 1.0 wt% to a Pd nanoparticle-supported strongly basic monolithic anion exchanger with a palladium loading of 1.0 wt%. The reaction product was 2-aminobiphenyl, and the conversion rate was 11%.

[0195] (Comparative Example 1-3: Hydrogenation reduction reaction of 2-nitrobiphenyl) The reaction was carried out in the same manner as in Examples 1-3, except that the catalyst used was changed from a Pd ion-supported weakly basic monolithic anion exchanger with a palladium loading of 1.0 wt% to a Pd nanoparticle-supported strongly acidic monolithic cation exchanger with a palladium loading of 1.0 wt%. The reaction product was 2-aminobiphenyl, and the conversion rate to 2-aminobiphenyl after 3 hours of reaction was 2%.

[0196] (Examples 1-5: Hydrogenation Reduction Reaction of 1-Carbobenzoxypiperazine) A resin-made cylindrical column was filled with a weakly basic monolithic anion exchanger carrying Pd ions with a palladium loading of 1.0 wt% (size of the cut-out catalyst: diameter 4.6 mm × length 30 mm (when immersed in water)). Next, a substrate solution was prepared by dissolving 6.0 mmol of 1-carbobenzoxypiperazine in 20 mL of ethanol. The temperature of the column was set to 80 °C, pressurized to 0.3 MPa with a back pressure valve, and supplied at a substrate solution flow rate of 0.5 mL / min and a hydrogen gas flow rate of 10 mL / min to conduct a hydrogenation reduction reaction. At this time, SV of the substrate solution was 60 h -1 It was. Also, the total contact time between the substrate solution and the catalyst layer was 1 minute. The reaction product was piperazine, and the conversion rate to piperazine after 3 h of the reaction was 69%.

[0197] (Examples 1-6: Hydrogenation Reduction Reaction of 1-Carbobenzoxypiperazine) The same method as in Examples 1-5 was used except that the column temperature was changed from 80 °C to 60 °C and the pressure was changed from 0.3 MPa to atmospheric pressure. The reaction product was piperazine, and the conversion rate was 95%.

[0198] (Comparative Examples 1-4: Hydrogenation Reduction Reaction of 1-Carbobenzoxypiperazine) The same method as in Examples 1-5 was used except that the catalyst used was changed from a weakly basic monolithic anion exchanger carrying Pd ions with a palladium loading of 1.0 wt% to a strongly basic monolithic anion exchanger carrying Pd nanoparticles with a palladium loading of 1.0 wt%. The reaction product was piperazine, and the conversion rate was 23%.

[0199] (Comparative Examples 1-5: Hydrogenation Reduction Reaction of 1-Carbobenzoxypiperazine) The same method as in Examples 1-5 was used except that the catalyst used was changed from a weakly basic monolithic anion exchanger carrying Pd ions with a palladium loading of 1.0 wt% to a strongly acidic monolithic cation exchanger carrying Pd nanoparticles with a palladium loading of 1.0 wt%. The reaction product was piperazine, and the conversion rate was 0%.

[0200] (Examples 1-7: Hydrogenation Reduction Reaction of Benzyl Benzoate) A weakly basic monolithic anion exchanger loaded with Pd ions with a palladium loading of 1.0 wt% was packed into a cylindrical column made of resin (size of the cut-out catalyst: diameter 4.6 mm × length 30 mm (when immersed in water)). Next, a substrate solution was prepared by dissolving 6.0 mmol of benzyl benzoate in 20 mL of ethanol. The temperature of the column was set at 80°C, pressurized to 0.3 MPa with a back pressure valve, and supplied at a substrate solution flow rate of 0.5 mL / min and a hydrogen gas flow rate of 10 mL / min to conduct a hydrogenation reduction reaction. At this time, the SV of the substrate solution was 60 h -1 It was. Also, the total contact time between the substrate solution and the catalyst layer was 1 minute. The reaction product was benzoic acid, and the conversion rate to benzoic acid after 3 h of the reaction was 96%.

[0201] (Examples 1-8: Hydrogenation Reduction Reaction of Benzyl Benzoate) It was carried out in the same manner as in Examples 1-7 except that the column temperature was changed from 80°C to 60°C and the pressure was changed from 0.3 MPa to atmospheric pressure. The reaction product was benzoic acid, and the conversion rate was 82%.

[0202] (Examples 1-9: Hydrogenation Reduction Reaction of Acetophenone) A weakly basic monolithic anion exchanger loaded with Pd ions with a palladium loading of 1.0 wt% was packed into a cylindrical column made of resin (size of the cut-out catalyst: diameter 4.6 mm × length 30 mm (when immersed in water)). Next, a substrate solution was prepared by dissolving 6.0 mmol of acetophenone in 20 mL of ethanol. The temperature of the column was set at 80°C, pressurized to 0.3 MPa with a back pressure valve, and supplied at a substrate solution flow rate of 0.5 mL / min and a hydrogen gas flow rate of 10 mL / min to conduct a hydrogenation reduction reaction. At this time, the SV of the substrate solution was 60 h -1 It was. Also, the total contact time between the substrate solution and the catalyst layer was 1 minute. The reaction product was 1-phenylethanol, and the conversion rate to 1-phenylethanol after 3 h of the reaction was 15%.

[0203] (Examples 1-10: Hydrogenation Reduction Reaction of Acetophenone) It was carried out in the same manner as in Examples 1-9, except that the column temperature was changed from 80 °C to 60 °C and the pressure was changed from 0.3 MPa to atmospheric pressure. The reaction product was 1-phenylethanol, and the conversion rate was 8%.

[0204] (Comparative Examples 1-6: Hydrogenation reduction reaction of acetophenone) It was carried out in the same manner as in Examples 1-9, except that the catalyst used was changed from a weakly basic monolith anion exchanger supporting Pd ions with a Pd loading of 1.0 wt% to a strongly basic monolith anion exchanger supporting Pd nanoparticles with a Pd loading of 1.0 wt%, but there was no reaction.

[0205] (Examples 1-11: Hydrogenation reduction reaction of 4-(benzyloxy)phenol) A cylindrical column made of resin was filled with a weakly basic monolith anion exchanger supporting Pd ions with a Pd loading of 1.0 wt% (the size of the cut-out catalyst: diameter 4.6 mm × length 30 mm (when immersed in water)). Next, a substrate solution was prepared by dissolving 6.0 mmol of 4-(benzyloxy)phenol in 20 mL of ethanol. The column temperature was set to 80 °C, and the pressure was increased to 0.3 MPa using a back pressure valve. The substrate solution was supplied at a flow rate of 0.5 mL / min and hydrogen gas was supplied at a flow rate of 10 mL / min to carry out the hydrogenation reduction reaction. At this time, the SV of the substrate solution was 60 h -1 It was. Also, the total contact time between the substrate solution and the catalyst layer was 1 minute. The reaction product was hydroquinone, and the conversion rate to hydroquinone after 3 h of the reaction was 82%.

[0206]

Table 1

[0207] From the results in Table 1, it was revealed that the catalyst using a weakly basic monolith anion exchanger as the carrier had the highest hydrogenation reduction activity in all cases of using any substrate.

[0208] [Catalytic hydrogenation reduction by continuous flow method] (Example 2-1: Hydrogenation reduction reaction of diphenylacetylene) A resin-made cylindrical column was filled with a weakly basic monolithic anion exchanger carrying Pd ions with a palladium loading of 1.0 wt% (size of the cut-out catalyst: diameter 4.6 mm × length 30 mm (when immersed in water)). Next, a substrate solution was prepared by making diphenylacetylene 0.3 mol / L in an ethanol solution. The temperature of the column was set at 80°C, pressurized to 0.3 MPa with a back pressure valve, and supplied at a substrate solution flow rate of 0.5 mL / min and a hydrogen gas flow rate of 10 mL / min to conduct a hydrogenation reduction reaction. At this time, the SV of the substrate solution was 60 h -1 It was. Also, the total contact time between the substrate solution and the catalyst layer was 1 minute. The reaction products were 1,2-diphenylethane and cis-stilbene, and the ratios of 1,2-diphenylethane and cis-stilbene after 2 h of liquid passing were 99% and 1% respectively. The conversion rate was 100%.

[0209] (Example 2-2: Hydrogenation reduction reaction of 2-nitrobiphenyl) A resin-made cylindrical column was filled with a weakly basic monolithic anion exchanger carrying Pd ions with a palladium loading of 1.0 wt% (size of the cut-out catalyst: diameter 4.6 mm × length 30 mm (when immersed in water)). Next, a substrate solution was prepared by making 2-nitrobiphenyl 0.3 mol / L in an ethanol solution. The temperature of the column was set at 80°C, pressurized to 0.3 MPa with a back pressure valve, and supplied at a substrate solution flow rate of 0.5 mL / min and a hydrogen gas flow rate of 10 mL / min to conduct a hydrogenation reduction reaction. At this time, the SV of the substrate solution was 60 h -1 It was. Also, the total contact time between the substrate solution and the catalyst layer was 1 minute. The reaction product was 2-aminobiphenyl, and the conversion rate after 2 h of liquid passing was 56%.

[0210] (Example 2-3: Hydrogenation reduction reaction of 2-nitrobiphenyl) The catalyst used was changed from a weakly basic monolithic anion exchanger supported with Pd ions having a palladium loading of 1.0 wt% (size of the cut-out catalyst: diameter 4.6 mm × length 30 mm (when immersed in water)) to a weakly basic monolithic anion exchanger supported with Pd ions having a palladium loading of 0.2 wt% (size of the cut-out catalyst: diameter 4.6 mm × length 150 mm (when immersed in water)). The hydrogen gas flow rate was changed from 10 mL / min to 25 mL / min. Otherwise, the procedure was the same as in Example 2-2. The reaction product was 2-aminobiphenyl, and the conversion rate was 100%.

[0211] (Example 2-4: Hydrogenation reduction reaction of 2-nitrobiphenyl) The procedure was the same as in Example 2-2, except that the column temperature was changed from 80 °C to 60 °C and the pressure was changed from 0.3 MPa to atmospheric pressure. The reaction product was 2-aminobiphenyl, and the conversion rate was 88%.

[0212] (Example 2-5: Hydrogenation reduction reaction of 1-carbobenzoxypiperazine) A weakly basic monolithic anion exchanger supported with Pd ions having a palladium loading of 1.0 wt% was packed into a cylindrical column made of resin (size of the cut-out catalyst: diameter 4.6 mm × length 30 mm (when immersed in water)). Then, a substrate solution was prepared by making 1-carbobenzoxypiperazine 0.3 mol / L in an ethanol solution. The temperature of the column was set to 80 °C, and the pressure was increased to 0.3 MPa using a back pressure valve. The substrate solution was supplied at a flow rate of 0.5 mL / min and hydrogen gas was supplied at a flow rate of 10 mL / min to conduct the hydrogenation reduction reaction. At this time, the space velocity (SV) of the substrate solution was 60 h -1 The total contact time between the substrate solution and the catalyst layer was 1 minute. The reaction product was piperazine, and the conversion rate after 2 h of liquid passing was 61%.

[0213] (Example 2-6: Hydrogenation reduction reaction of 1-carbobenzoxypiperazine) The procedure was the same as in Example 2-2, except that the column temperature was changed from 80 °C to 60 °C and the pressure was changed from 0.3 MPa to atmospheric pressure. The reaction product was piperazine, and the conversion rate was 82%.

[0214] (Example 2-7: Hydrogenation Reduction Reaction of Acetophenone) A weakly basic monolithic anion exchanger loaded with Pd ions with a palladium loading of 10.0 wt% was packed into a cylindrical column made of resin (size of the cut-out catalyst: diameter 4.6 mm × length 30 mm (when immersed in water)). A substrate solution was prepared by making acetophenone 0.3 mol / L in an ethanol solution. The temperature of the column was set at 80 °C, pressurized to 0.3 MPa with a back pressure valve, and supplied at a substrate solution flow rate of 0.5 mL / min and a hydrogen gas flow rate of 10 mL / min to carry out the hydrogenation reduction reaction. At this time, the SV of the substrate solution was 60 h -1 It was. Also, the total contact time between the substrate solution and the catalyst layer was 1 minute. The reaction product was 1-phenylethanol, and the conversion rate after 2 h of liquid passing was 11%.

[0215] (Example 2-8: Hydrogenation Reduction Reaction of Nitrobenzene) A weakly basic monolithic anion exchanger loaded with Pd ions with a palladium loading of 1.0 wt% was packed into a cylindrical column made of resin (size of the cut-out catalyst: diameter 4.6 mm × length 30 mm (when immersed in water)). Next, a substrate solution was prepared by making nitrobenzene 0.3 mol / L in a toluene solution, and a weakly basic monolithic anion exchanger loaded with Pd ions with a palladium loading of 1.0 wt% was packed into the column (size of the cut-out catalyst: diameter 4.6 mm × length 30 mm (when immersed in water)). The temperature of the column was set at 80 °C, pressurized to 0.3 MPa with a back pressure valve, and supplied at a substrate solution flow rate of 0.5 mL / min and a hydrogen gas flow rate of 25 mL / min to carry out the hydrogenation reduction reaction. At this time, the SV of the substrate solution was 60 h -1 It was. Also, the total contact time between the substrate solution and the catalyst layer was 1 minute. The reaction product was aniline, and the conversion rate after 2 h of liquid passing was 97%.

[0216] (Example 2-9: Hydrogenation Reduction Reaction of Nitrobenzene) It was carried out in the same manner as in Example 2-8 except that the solvent was changed from toluene to ethyl acetate. The reaction product was aniline, and the conversion rate was 98%.

[0217] (Example 2-10: Hydrogenation Reduction Reaction of Nitrobenzene) The reaction was carried out in the same manner as in Example 2-8 except that the solvent was changed from toluene to THF. The reaction product was aniline, and the conversion rate was 100%.

[0218] (Example 2-11: Hydrogenation Reduction Reaction of Nitrobenzene) The reaction was carried out in the same manner as in Example 2-8 except that the catalyst used was changed from a Pd ion-supported weakly basic monolith anion exchanger with a palladium loading of 1.0 wt% (size of the cut-out catalyst: diameter 4.6 mm × length 30 mm (when immersed in water)) to a Pt ion-supported weakly basic monolith anion exchanger with a platinum loading of 1.0 wt% (size of the cut-out catalyst: diameter 4.6 mm × length 30 mm (when immersed in water)), and the solvent was changed from toluene to ethanol. The reaction product was aniline, and the conversion rate was 83%.

[0219] [Table 2]

[0220] It was revealed from Table 2 that good hydrogenation reduction activity was shown even when the catalyst amount, noble metal loading, solvent, temperature, pressure, and hydrogen flow rate were changed.

[0221] [Batch-Type Catalytic Hydrogenation Reduction] (Example 3-1: Hydrogenation Reduction Reaction of Acetophenone) 0.24 g (2 mmol) of acetophenone and 6.7 mL of ethanol were added to a pressure vessel. Then, 33 mg of the powdered 1.0 wt% Pd-supported catalyst prepared above, in an amount such that the amount of palladium was 0.16 mol% with respect to the reaction substrate, was added, and hydrogen gas was sealed in the pressure vessel at 0.3 MPa, and the reaction was carried out at 80 °C for 3 hours. The reaction product was 1-phenylethanol, and the conversion rate was 10%.

[0222] (Example 3-2: Deprotection Reaction of 1-Carbobenzoxypiperazine) Instead of using the substrate solution prepared by dissolving 2 mmol of acetophenone in 6.7 mL of methanol, a substrate solution prepared by dissolving 0.44 g (2 mmol) of 1-carbobenzoxypiperazine in 6.7 mL of methanol was used, and the procedure was the same as in Example 3-1. The reaction product was piperazine, and the conversion rate was 100%.

[0223] (Example 3-3: Hydrogenation Reduction Reaction of 2-Nitrobiphenyl) Instead of using the substrate solution prepared by dissolving 2 mmol of acetophenone in 6.7 mL of methanol, a substrate solution prepared by dissolving 0.40 g (2 mmol) of 2-nitrobiphenyl in 6.7 mL of methanol was used, and the procedure was the same as in Example 3-1. The reaction product was 2-aminobiphenyl, and the conversion rate was 24%.

[0224] (Example 3-4: Hydrogenation Reduction Reaction of Benzyl Benzoate) Instead of using the substrate solution prepared by dissolving 2 mmol of acetophenone in 6.7 mL of methanol, a substrate solution prepared by dissolving 0.42 g (2 mmol) of benzyl benzoate in 6.7 mL of methanol was used, and the procedure was the same as in Example 3-1. The reaction product was benzoic acid, and the conversion rate was 100%.

[0225] (Example 3-5: Hydrogenation Reduction Reaction of Diphenylacetylene) The hydrogenation reduction reaction of diphenylacetylene was carried out. 0.36 g (2 mmol) of diphenylacetylene was added to 20 mL of ethanol, and 100 mg of the above-prepared powdered 1.0 wt% Pd-supported catalyst was added in an amount such that the amount of palladium was 0.16 mol% with respect to the reaction substrate. Hydrogen gas was supplied from a balloon, and the reaction was carried out at atmospheric pressure and 60 °C for 2 hours. The reaction products were 1,2-diphenylethane and stilbene, and the ratios of 1,2-diphenylethane and stilbene were 97% and 3%, respectively.

[0226]

Table 3

[0227] From Table 3, it was revealed that not only the flow-type reaction but also the batch-type reaction exhibited good hydrogenation reduction activity.

[0228] [Catalytic Hydrogenation Reduction of Nitrobenzene by Long-Term Continuous Operation] (Example 4-1: Hydrogenation Reduction Reaction of Nitrobenzene Using a Pt Catalyst) A weakly basic monolithic anion exchanger loaded with Pt ions with a Pt loading of 0.57 wt% was packed into a resin cylindrical column (the size of the cut-out catalyst: diameter 4.6 mm × length 30 mm (when immersed in water)). Then, a substrate solution was prepared by making nitrobenzene 0.3 mol / L in an ethanol solution. The temperature of the column was set at 80°C, pressurized to 0.3 MPa with a back pressure valve, and supplied at a substrate solution flow rate of 0.5 mL / min and a hydrogen gas flow rate of 25 mL / min to conduct the hydrogenation reduction reaction. At this time, the SV of the substrate solution was 60 h -1 The total contact time between the substrate solution and the catalyst layer was 1 minute. The flow rate of the 0.3 mol / L nitrobenzene / ethanol solution after 24 h of liquid flow was 720 mL. The reaction product was aniline, and the total conversion rate to aniline after 24 h of liquid flow was 90%. Also, the TON (turnover number of the catalyst) at this time was approximately 67000.

[0229] (Example 4-2: Hydrogenation Reduction Reaction of Nitrobenzene Using a Pt Catalyst) A weakly basic monolithic anion exchanger loaded with Pt ions with a Pt loading of 0.57 wt% was packed into a resin cylindrical column (the size of the cut-out catalyst: diameter 6.0 mm × length 90 mm (when immersed in water)). Then, a substrate solution was prepared by making nitrobenzene 0.2 mol / L in an ethanol solution. The temperature of the column was set at 80°C, pressurized to 0.3 MPa with a back pressure valve, and supplied at a substrate solution flow rate of 0.2 mL / min and a hydrogen gas flow rate of 7 mL / min to conduct the hydrogenation reduction reaction. At this time, the SV of the substrate solution was 8 h -1It was so. Also, the total time for which the substrate solution and the catalyst layer were in contact was 7.5 minutes. The amount of the 0.2 mol / L nitrobenzene / ethanol solution passed through after 24 hours of liquid flow was 288 mL. The reaction product was aniline, and the total conversion rate to aniline after 24 hours of liquid flow was 100%. Also, the TON (turnover number of the catalyst) at this time was approximately 2200. After washing the Pt ion-supported weakly basic monolith anion exchanger after use with ethanol and drying it under reduced pressure, analysis of the Pt particle size was performed by TEM analysis. The analysis results are shown in Fig. 16.

[0230] (Example 4-3: Hydrogenation reduction reaction of nitrobenzene using a Pd catalyst) A Pd ion-supported weakly basic monolith anion exchanger with a palladium loading of 1.0 wt% was packed into a cylindrical column made of resin (size of the cut-out catalyst: diameter 4.6 mm × length 30 mm (when immersed in water)). Next, a substrate solution was prepared by making nitrobenzene 0.3 mol / L in a toluene solution, the temperature of the column was set to 80°C, pressurized to 0.3 MPa with a back pressure valve, and supplied at a substrate solution flow rate of 0.5 mL / min and a hydrogen gas flow rate of 25 mL / min to carry out a hydrogenation reduction reaction. At this time, the SV of the substrate solution was 60 h -1 It was so. Also, the total time for which the substrate solution and the catalyst layer were in contact was 1 minute. The amount of the 0.3 mol / L nitrobenzene / toluene solution passed through after 20 hours of liquid flow was 600 mL. The reaction product was aniline, and the total conversion rate to aniline after 20 hours of liquid flow was 100%. Also, the TON (turnover number of the catalyst) at this time was approximately 19000.

[0231]

Table 4

[0232] From Table 4, it became clear that even when a long-term hydrogenation reduction reaction was carried out, good hydrogenation reduction activity was exhibited without a decrease in the catalyst activity.

[0233] (Example 5-1: Hydrogenation reduction reaction of 2-nitrobiphenyl, flow rate 1 mL / min to 5 mL / min) A weakly basic monolithic anion exchanger loaded with Pd ions with a palladium loading of 1.0 wt% was packed into a cylindrical column made of resin (the size of the cut-out catalyst: diameter 4.6 mm × length 30 mm (when immersed in water)). Subsequently, a substrate solution was prepared by making 2-nitrobiphenyl into a 0.3 mol / L solution in an ethanol solution, and a weakly basic monolithic anion exchanger loaded with Pd ions with a palladium loading of 1.0 wt% was packed (the size of the cut-out catalyst: diameter 4.6 mm × length 30 mm (when immersed in water)). The temperature of the column was set at 80°C, pressurized to 0.3 MPa to 0.5 MPa with a back pressure valve, and supplied at a substrate solution flow rate of 1 mL / min to 10 mL / min and a hydrogen gas flow rate of 50 mL / min to 100 mL to carry out a hydrogenation reduction reaction. The experimental results are shown in Table 5.

[0234]

Table 5

[0235] (Example 6-1: Preparation of a Pt catalyst using hydrazine as a reducing agent and hydrogenation reduction reaction of 2-nitrobiphenyl) A platinum group metal-supported catalyst (a weakly basic monolithic anion exchanger loaded with Pt ions) was reduced with a 3% hydrazine monohydrate aqueous solution, and the obtained weakly basic monolithic anion exchanger loaded with Pt nanoparticles was washed several times with pure water and then dried by vacuum drying to obtain a black weakly basic monolithic anion exchanger loaded with Pt nanoparticles.

[0236] The obtained weakly basic monolithic anion exchanger loaded with Pt nanoparticles was packed into a cylindrical column made of resin (the size of the cut-out catalyst: diameter 4.6 mm × length 30 mm (when immersed in water)). Subsequently, a substrate solution was prepared by making 2-nitrobenzene into a 0.3 mol / L solution in an ethanol solution, the temperature of the column was set at 80°C, pressurized to 0.3 MPa with a back pressure valve, and supplied at a substrate solution flow rate of 0.5 mL / min and a hydrogen gas flow rate of 25 mL / min to carry out a hydrogenation reduction reaction. At this time, the SV of the substrate solution was 60 h -1It was so. Also, the total time during which the substrate solution and the catalyst layer were in contact was 1 minute. The reaction product was 2-aminobiphenyl, and the conversion rate to 2-aminobiphenyl after 0.5 h of liquid flow was 48%.

[0237] (Example 6-2: Preparation of a Pt catalyst using sodium borohydride as a reducing agent and hydrogenation reduction reaction of 2-nitrobiphenyl) An aqueous solution of 1 mol / L sodium borohydride was added to a platinum group metal-supported catalyst (Pt ion-supported weakly basic monolith anion exchanger), and the mixture was stirred overnight at room temperature to obtain a weakly basic monolith anion exchanger supported with Pt nanoparticles. After the obtained weakly basic monolith anion exchanger supported with Pt nanoparticles was washed several times with pure water and then dried by drying under reduced pressure, a black weakly basic monolith anion exchanger supported with Pt nanoparticles was obtained.

[0238] The obtained weakly basic monolith anion exchanger supported with Pt nanoparticles was packed into a resin cylindrical column (size of the cut-out catalyst: diameter 4.6 mm × length 30 mm (when immersed in water)). Next, a substrate solution was prepared such that 2-nitrobenzene was 0.3 mol / L in an ethanol solution, the temperature of the column was set to 80°C, the pressure was increased to 0.3 MPa with a back pressure valve, and the substrate solution was supplied at a flow rate of 0.5 mL / min and hydrogen gas at a flow rate of 25 mL / min to conduct a hydrogenation reduction reaction. At this time, the SV of the substrate solution was 60 h -1 It was so. Also, the total time during which the substrate solution and the catalyst layer were in contact was 1 minute. The reaction product was 2-aminobiphenyl, and the conversion rate to 2-aminobiphenyl after 0.5 h of liquid flow was 96%.

[0239] (Example 6-3: Preparation of a Pt catalyst using ethanol / water as a reducing agent and hydrogenation reduction reaction of 2-nitrobiphenyl) 30 mL of ethanol and 30 mL of water were added to a platinum group metal-supported catalyst (weak basic monolith anion exchanger supported with Pt ions), and the mixture was heated and stirred for 3 hours under reflux conditions to obtain a weak basic monolith anion exchanger supported with Pt nanoparticles. After washing the obtained weak basic monolith anion exchanger supported with Pt nanoparticles several times with pure water, it was dried by drying under reduced pressure to obtain a black weak basic monolith anion exchanger supported with Pt nanoparticles.

[0240] The obtained weak basic monolith anion exchanger supported with Pt nanoparticles was packed into a cylindrical column made of resin (the size of the cut-out catalyst: diameter 4.6 mm × length 30 mm (when immersed in water)). Next, a substrate solution was prepared by making 2-nitrobenzene 0.3 mol / L in an ethanol solution. The temperature of the column was set at 80 °C, pressurized to 0.3 MPa with a back pressure valve, and supplied at a substrate solution flow rate of 0.5 mL / min and a hydrogen gas flow rate of 25 mL / min to conduct a hydrogenation reduction reaction. At this time, the space velocity (SV) of the substrate solution was 60 h -1 The total contact time between the substrate solution and the catalyst layer was 1 minute. The reaction product was 2-aminobiphenyl, and the conversion rate to 2-aminobiphenyl after 0.5 h of liquid passing was 98%.

[0241] (Example 6-4: Preparation of a Pt catalyst using methanol / water as a reducing agent and hydrogenation reduction reaction of 2-nitro-biphenyl) 30 mL of methanol and 30 mL of water were added to a platinum group metal-supported catalyst (weak basic monolith anion exchanger supported with Pt ions), and the mixture was heated and stirred for 3 hours under reflux conditions to obtain a weak basic monolith anion exchanger supported with Pt nanoparticles. After washing the obtained weak basic monolith anion exchanger supported with Pt nanoparticles several times with pure water, it was dried by drying under reduced pressure to obtain a black weak basic monolith anion exchanger supported with Pt nanoparticles.

[0242] The obtained weakly basic monolithic anion exchanger supporting Pt nanoparticles was packed into a cylindrical column made of resin (size of the cut-out catalyst: diameter 4.6 mm × length 30 mm (when immersed in water)). Subsequently, a substrate solution was prepared by making 2-nitrobenzene 0.3 mol / L in an ethanol solution. The temperature of the column was set at 80 °C, and the pressure was increased to 0.3 MPa with a back pressure valve. The substrate solution was supplied at a flow rate of 0.5 mL / min and hydrogen gas at a flow rate of 25 mL / min to conduct a hydrogenation reduction reaction. At this time, the SV of the substrate solution was 60 h -1 was obtained. Also, the total contact time between the substrate solution and the catalyst layer was 1 minute. The reaction product was 2-aminobiphenyl, and the conversion rate to 2-aminobiphenyl after 0.5 h of liquid passing was 40%.

[0243]

Table 6

[0244] From Table 6, it became clear that good hydrogenation reduction activity was shown even when platinum was reduced with various reducing agents.

[0245] As described above, by the catalytic hydrogenation reduction method of the examples, the catalytic hydrogenation reduction reaction could be carried out at a high conversion rate.

Explanation of symbols

[0246] 1 Skeletal phase, 2 Pore phase, 10 Co-continuous structure, 11 Rectangular image region, 12 Skeletal part, 13 Macropore, 21 Skeletal surface, 22a, 22b, 22c, 22d, 22e Protrusions, 50 Catalytic hydrogenation reduction device, 52 Reaction vessel, 54 Reaction substrate vessel, 56 Reaction solution receiver, 58 Reaction substrate supply pump, 60 Mixer, 62 Switching valve, 64 Hydrogen source supply pipe, 66 Reaction substrate supply pipe, 68 Reaction solution discharge pipe, 70 Circulation pipe.

Claims

1. A catalytic hydrogenation reduction method for subjecting a reaction substrate and a hydrogen source to contact hydrogenation reduction in the presence of a platinum group metal-supported catalyst, wherein the platinum group metal-supported catalyst is a platinum group metal-supported catalyst in which at least one of platinum group metal ions, platinum group metal complex ions, and platinum group metal nanoparticles having an average particle diameter in the range of 1 to 100 nm is supported on an ion exchanger, the ion exchanger is composed of a continuous skeletal phase and a continuous pore phase, the thickness of the continuous skeleton is in the range of 1 to 100 μm, the average diameter of the continuous pores is in the range of 1 to 1000 μm, the total pore volume is in the range of 0.5 to 50 mL / g, the ion exchange capacity per weight in the dry state is in the range of 1 to 9 meq / g, and the ion exchange groups are distributed in the ion exchanger. The catalytic hydrogenation reduction method is characterized by being a monolithic weakly basic organic porous ion exchanger.

2. The catalytic hydrogenation reduction method according to claim 1, wherein the monolithic weakly basic organic porous ion exchanger has a continuous macropore structure in which macropores connected to each other and common openings having an average diameter in the range of 1 to 1000 μm are formed in the walls of the macropores, the total pore volume is in the range of 1 to 50 mL / g, the ion exchange capacity per weight in the dry state is in the range of 1 to 9 meq / g, and the ion exchange groups are distributed in the organic porous ion exchanger. The catalytic hydrogenation reduction method is characterized by this.

3. The catalytic hydrogenation reduction method according to claim 1, wherein the monolithic weakly basic organic porous ion exchanger is formed by aggregation of organic polymer particles having an average particle diameter in the range of 1 to 50 μm to form a three-dimensionally continuous skeletal portion, and three-dimensionally continuous pores having an average diameter in the range of 20 to 100 μm are formed between the skeletons. The total pore volume is in the range of 1 to 10 mL / g, the ion exchange capacity per weight in the dry state is in the range of 1 to 9 meq / g, and the ion exchange groups are distributed in the organic porous ion exchanger. The catalytic hydrogenation reduction method is characterized by this.

4. The catalytic hydrogenation reduction method according to claim 1, wherein The monolithic weakly basic organic porous ion exchanger is a continuous macroporous structure in which bubble-like macropores overlap with each other, and the overlapping portion forms an opening with an average diameter in the range of 30 to 300 μm. The total pore volume is in the range of 0.5 to 10 mL / g, the ion exchange capacity per unit weight in the dry state is in the range of 1 to 9 meq / g, the ion exchange groups are distributed in the organic porous ion exchanger, and in the SEM image of the cross-section of the continuous macroporous structure, the area of the skeleton portion appearing in the cross-section is in the range of 25 to 50% of the image area. A catalytic hydrogenation reduction method characterized by this.

5. The catalytic hydrogenation reduction method according to claim 1, wherein the monolithic weakly basic organic porous ion exchanger is composed of an aromatic vinyl polymer containing a cross-linked structural unit in the range of 0.1 to 5.0 mol% in all constituent units into which ion exchange groups are introduced, and has a three-dimensionally continuous skeleton with a thickness in the range of 1 to 60 μm, and three-dimensionally continuous pores with an average diameter in the range of 10 to 200 μm between the skeletons. It is a co-continuous structure, the total pore volume is in the range of 0.5 to 10 mL / g, the ion exchange capacity per unit weight in the dry state is in the range of 1 to 9 meq / g, and the ion exchange groups are distributed in the organic porous ion exchanger. A catalytic hydrogenation reduction method characterized by this.

6. The catalytic hydrogenation reduction method according to claim 1, wherein the monolithic weakly basic organic porous ion exchanger consists of a continuous skeleton phase and a continuous pore phase. The skeleton has a plurality of particulate bodies with a diameter in the range of 4 to 40 μm fixed to the surface or a plurality of protrusions with a size in the range of 4 to 40 μm formed on the skeleton surface of the organic porous ion exchanger. The average diameter of the continuous pores is in the range of 10 to 200 μm, the total pore volume is in the range of 0.5 to 10 mL / g, the ion exchange capacity per unit weight in the dry state is in the range of 1 to 9 meq / g, and the ion exchange groups are distributed in the organic porous ion exchanger. A catalytic hydrogenation reduction method characterized by this.

7. The catalytic hydrogenation reduction method according to any one of claims 1 to 6, wherein the loading amount of at least one of the platinum group metal ions, the platinum group metal complex ions, and the platinum group metal nanoparticles is in the range of 0.01 to 10% by mass in terms of platinum group metal atoms. A catalytic hydrogenation reduction method characterized by this.

8. A catalytic hydrogenation reduction method according to any one of claims 1 to 7, wherein the reaction substrate and the hydrogen source are continuously supplied to a reaction vessel filled with the platinum group metal-supported catalyst, and the reaction substrate and the hydrogen source are continuously brought into contact with each other in the presence of the platinum group metal-supported catalyst to perform catalytic hydrogenation reduction of the reaction substrate.

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