Method for producing 1,3-butanediol

Abstract

A method for producing 1,3-butanediol, the method comprising: a step for bringing a raw material liquid containing acetaldehyde into contact with a solid base catalyst and a hydrogenation catalyst to obtain a reaction liquid containing 1,3-butanediol, wherein the solid base catalyst includes at least one among metal elements having an atomic number of 12-20, and the hydrogenation catalyst includes Ni.

Description

Method for producing 1,3-butanediol

[0001] The present disclosure relates to a method for producing 1,3-butanediol.

[0002] 1,3-Butanediol (1,3-butylene glycol) is used in a wide range of applications, such as as a raw material for various synthetic resins, a raw material for surfactants, and an ingredient in cosmetics.

[0003] Conventionally, 1,3-butanediol has been produced by hydrogenating acetaldol, and for example, Patent Document 1 discloses a method for producing high-purity 1,3-butanediol from acetaldol.

[0004] Japanese Patent Application Laid-Open No. 2021-038189

[0005] In a conventional method, for example, acetaldol is produced from acetaldehyde using a base catalyst, followed by neutralization and separation steps, and then the acetaldol is hydrogenated using a Raney nickel catalyst to produce 1,3-butanediol.

[0006] An object of the present disclosure is to provide a method for producing 1,3-butanediol that can efficiently produce 1,3-butanediol from acetaldehyde in a short number of steps.

[0007] The present disclosure provides, for example, the following [1] to [8]. [1] A method for producing 1,3-butanediol, comprising the step of contacting a raw material liquid containing acetaldehyde with a solid base catalyst and a hydrogenation catalyst to obtain a reaction liquid containing 1,3-butanediol, wherein the solid base catalyst contains at least one metal element having an atomic number of 12 to 20, and the hydrogenation catalyst contains Ni. [2] The production method according to [1], wherein the step comprises a first step of contacting the raw material liquid with the solid base catalyst to obtain a mixed liquid containing acetaldehyde, and a second step of contacting the mixed liquid with the hydrogenation catalyst to obtain the reaction liquid. [3] The production method according to [1], wherein the step comprises contacting the raw material liquid with a mixture of the solid base catalyst and the hydrogenation catalyst to obtain the reaction liquid. [4] The production method according to [1], wherein the step comprises flowing the raw material liquid through a reactor equipped with a first catalyst layer containing the solid base catalyst and a second catalyst layer containing the hydrogenation catalyst to obtain the reaction liquid. [5] The production method according to any one of [1] to [4], wherein the raw material liquid contains at least one polar solvent selected from the group consisting of ethanol and water. [6] The production method according to [5], wherein the molar ratio of the polar solvent to acetaldehyde in the raw material liquid (polar solvent / acetaldehyde) is 0.3 or more. [7] The production method according to any one of [1] to [6], wherein the solid base catalyst comprises a support and a supported metal supported on the support, and the supported metal contains at least one metal element having an atomic number of 12 to 20. [8] The production method according to any one of [1] to [7], wherein the solid base catalyst contains an inorganic oxide containing at least one metal element selected from the group consisting of Mg and Al.

[0008] According to the present disclosure, there is provided a method for producing 1,3-butanediol, which can efficiently produce 1,3-butanediol from acetaldehyde in a short number of steps.

[0009] Preferred embodiments of the present disclosure will be described in detail below.

[0010] The method for producing 1,3-butanediol of this embodiment is a method for producing 1,3-butanediol from acetaldehyde using a solid base catalyst and a hydrogenation catalyst. That is, the method for producing 1,3-butanediol of this embodiment may include a step of contacting a raw material liquid containing acetaldehyde with the solid base catalyst and the hydrogenation catalyst to obtain a reaction liquid containing 1,3-butanediol. In this embodiment, the solid base catalyst contains at least one metal element having an atomic number of 12 to 20, and the hydrogenation catalyst contains Ni.

[0011] The method for producing 1,3-butanediol of this embodiment combines a specific solid base catalyst with a specific hydrogenation catalyst, allowing 1,3-butanediol to be produced efficiently from acetaldehyde in a short process. Specifically, the method for producing 1,3-butanediol of this embodiment employs the specific solid base catalyst, allowing 1,3-butanediol to be produced by directly contacting the reaction product of acetaldehyde using the solid base catalyst with the hydrogenation catalyst without separation and purification. Therefore, the method for producing 1,3-butanediol of this embodiment can omit steps such as isolating and purifying intermediates (e.g., acetaldol, aldoxane, para-aldol, etc.), allowing 1,3-butanediol to be produced efficiently in a short process.

[0012] The solid base catalyst contains at least one metal element (hereinafter also referred to as metal element A) having an atomic number of 12 to 20. The metal element having an atomic number of 12 to 20 is an element that corresponds to a metal element among the elements having atomic numbers 12 to 20, and specifically indicates Mg (atomic number 12), Al (atomic number 13), K (atomic number 19), and Ca (atomic number 20).

[0013] The solid base catalyst may contain, for example, an inorganic oxide. The solid base catalyst may have, for example, an inorganic oxide support and a supported metal supported on the inorganic oxide support, the supported metal containing at least one metal element having an atomic number of 12 to 20. The solid base catalyst may also be, for example, an inorganic oxide containing at least one metal element having an atomic number of 12 to 20.

[0014] Preferred embodiments of the solid base catalyst will be described in detail below.

[0015] (Solid base catalyst (1)) The solid base catalyst of the first embodiment (hereinafter also referred to as solid base catalyst (1)) contains a support and a supported metal supported on the support. The solid base catalyst (1) contains, as the supported metal, at least one metal element having an atomic number of 12 to 20 (metal element A).

[0016] The support may be, for example, an inorganic oxide support. The inorganic oxide support is a support composed of an inorganic oxide. The inorganic oxide support may or may not contain a metal element with an atomic number of 12 to 20.

[0017] Examples of inorganic oxides constituting the inorganic oxide support include silica, alumina (e.g., γ-alumina), magnesia, calcia, and composite oxides thereof (e.g., silica-alumina, silica-magnesia, magnesia-alumina, calcia-alumina, silica-calcia, zeolite, etc.). Preferred inorganic oxides are silica, alumina, magnesia, and magnesia-alumina, and more preferred are silica and magnesia-alumina.

[0018] The carrier is preferably a porous carrier, more preferably a porous inorganic oxide carrier.

[0019] The specific surface area of ​​the carrier is, for example, 5 m ２ / g or more, and from the viewpoint of further improving the yield of 1,3-butanediol, 50 m ２ / g or more, 100m ２ / g or more, 150m ２ / g or more, 200m ２ / g or more, or 400m ２ The specific surface area of ​​the carrier may be, for example, 1000 m ２ / g or less, and ２ / g or less, 800m ２ / g or less, or 700m ２ That is, the specific surface area of ​​the carrier may be, for example, 5 to 1000 m ２ / g, 5-900m ２ / g, 5-800m２ / g, 5-700m ２ / g, 50-1000m ２ / g, 50-900m ２ / g, 50-800m ２ / g, 50-700m ２ / g, 100-1000m ２ / g, 100-900m ２ / g, 100-800m ２ / g, 100-700m ２ / g, 150-1000m ２ / g, 150-900m ２ / g, 150-800m ２ / g, 150-700m ２ / g, 200-1000m ２ / g, 200-900m ２ / g, 200-800m ２ / g, 200-700m ２ / g, 400-1000m ２ / g, 400-900m ２ / g, 400-800m ２ / g, or 400 to 700 m ２ / g.

[0020] In this specification, the specific surface area of ​​the carrier is a value measured by a nitrogen adsorption method.

[0021] The supported metal contains at least one metal element (metal element A) having an atomic number of 12 to 20. That is, the supported metal contains at least one selected from the group consisting of Mg (atomic number 12), Al (atomic number 13), K (atomic number 19), and Ca (atomic number 20), and it is particularly preferable that the supported metal contains Mg.

[0022] The supported metal may be present on the support as an oxide, an ion, or an elemental metal, but is preferably present on the support as an oxide.

[0023] The content of the supported metal (in terms of metal element) may be, for example, 1% by mass or more based on the total amount of the solid base catalyst (1), and from the viewpoint of further improving the yield of 1,3-butanediol, it may be 2% by mass or more, 3% by mass or more, 4% by mass or more, or 5% by mass or more. Furthermore, the content of the supported metal (in terms of metal element) may be, for example, 50% by mass or less based on the total amount of the solid base catalyst (1), and from the viewpoint of economic efficiency, it may be 30% by mass or less, 20% by mass or less, or 10% by mass or less. That is, the content of the supported metal (in terms of metal element) may be, for example, 1 to 50 mass%, 1 to 30 mass%, 1 to 20 mass%, 1 to 10 mass%, 2 to 50 mass%, 2 to 30 mass%, 2 to 20 mass%, 2 to 10 mass%, 3 to 50 mass%, 3 to 30 mass%, 3 to 20 mass%, 3 to 10 mass%, 4 to 50 mass%, 4 to 30 mass%, 4 to 20 mass%, 4 to 10 mass%, 5 to 50 mass%, 5 to 30 mass%, 5 to 20 mass%, or 5 to 10 mass%, based on the total amount of the solid base catalyst (1).

[0024] The supported metal may contain a metal element other than the metal element A, but preferably contains the metal element A as the main component. The content of the metal element A (in terms of metal element) may be, for example, 50 mass% or more, preferably 70 mass% or more, more preferably 90 mass% or more, and may be 95 mass% or more, 97 mass% or more, or 99 mass% or more, or may be 100 mass% based on the total amount of the supported metal.

[0025] The method for supporting the supported metal is not particularly limited, and the metal may be supported on the support by a known method, such as evaporation to dryness, pore volume method, incipient wetness method, coprecipitation method, etc.

[0026] (Solid base catalyst (2)) The solid base catalyst of the second embodiment (hereinafter referred to as solid base catalyst (2)) contains an inorganic oxide containing at least one metal element selected from the group consisting of Mg and Al. The inorganic oxide is preferably an inorganic oxide containing Mg.

[0027] The solid base catalyst (2) may be composed of the inorganic oxide, or may be composed of the inorganic oxide and a supported metal supported on the inorganic oxide.

[0028] The inorganic oxide in the solid base catalyst (2) may be, for example, magnesia, alumina (e.g., γ-alumina), or magnesia-alumina (preferably magnesia-alumina having a spinel structure). The inorganic oxide in the solid base catalyst (2) may also be, for example, a calcined product obtained by calcining hydrotalcite. Such a calcined product can be suitably used as magnesia-alumina having a spinel structure.

[0029] The inorganic oxide in the solid base catalyst (2) may further contain other metal elements or metalloid elements (e.g., B, Si, etc.) in addition to Mg and Al, but preferably contains an oxide of Mg and / or Al as the main component. In the solid base catalyst (2), the total content of Mg and Al in the inorganic oxide, calculated as oxide, may be, for example, 50 mass% or more, preferably 70 mass% or more, more preferably 90 mass% or more, and may be 95 mass% or more, 97 mass% or more, or 99 mass% or more, or may even be 100 mass%.

[0030] In the solid base catalyst (2), the specific surface area of ​​the inorganic oxide is, for example, 5 m ２ / g or more, and from the viewpoint of further improving the yield of 1,3-butanediol, 50 m ２ / g or more, 100m ２ / g or more, 150m ２ / g or more, 200m ２ / g or more, or 400m ２ The specific surface area of ​​the inorganic oxide may be, for example, 1000 m ２ / g or less, and from the viewpoint of production, ２ / g or less, 800m ２ / g or less, or 700m ２ That is, the specific surface area of ​​the inorganic oxide may be, for example, 5 to 1000 m ２ / g, 5-900m ２ / g, 5-800m ２ / g, 5-700m ２ / g, 50-1000m ２ / g, 50-900m ２ / g, 50-800m２ / g, 50-700m ２ / g, 100-1000m ２ / g, 100-900m ２ / g, 100-800m ２ / g, 100-700m ２ / g, 150-1000m ２ / g, 150-900m ２ / g, 150-800m ２ / g, 150-700m ２ / g, 200-1000m ２ / g, 200-900m ２ / g, 200-800m ２ / g, 200-700m ２ / g, 400-1000m ２ / g, 400-900m ２ / g, 400-800m ２ / g, or 400 to 700 m ２ / g.

[0031] In this specification, the specific surface area of ​​the inorganic oxide is measured in the same manner as the specific surface area of ​​the support described above.

[0032] When the solid base catalyst (2) has a supported metal, the supported metal may be, for example, a metal element (metal element A) having an atomic number of 12 to 20. That is, the supported metal may contain at least one metal element (metal element A) selected from the group consisting of Mg (atomic number 12), Al (atomic number 13), K (atomic number 19), and Ca (atomic number 20), and preferably contains Mg.

[0033] The supported metal may be present on the support as an oxide, an ion, or an elemental metal, but is preferably present on the support as an oxide.

[0034] When the solid base catalyst (2) has a supported metal, the content of the supported metal (in terms of metal element) may be, for example, 1 mass % or more, 2 mass % or more, 3 mass % or more, 4 mass % or more, or 5 mass % or more, based on the total amount of the solid base catalyst (2). Furthermore, the content of the supported metal in the solid base catalyst (2) (in terms of metal element) may be, for example, 50 mass % or less, 30 mass % or less, 20 mass % or less, or 10 mass % or less, based on the total amount of the solid base catalyst (2). That is, the content of the supported metal in the solid base catalyst (2) (metal element equivalent), based on the total amount of the solid base catalyst (2), for example, 0 to 50 mass%, 0 to 30 mass%, 0 to 20 mass%, 0 to 10 mass%, 1 to 50 mass%, 1 to 30 mass%, 1 to 20 mass%, 1 to 10 mass%, 2 to 50 mass%, 2 to 30 mass%, 2 to 20 mass%, 2 to 10 mass%, 3 to 50 mass%, 3 to 30 mass%, 3 to 20 mass%, 3 to 10 mass%, 4 to 50 mass%, 4 to 30 mass%, 4 to 20 mass%, 4 to 10 mass%, 5 to 50 mass%, 5 to 30 mass%, 5 to 20 mass%, or 5 to 10 mass%.

[0035] When the solid base catalyst (2) has a supported metal, the supported metal may contain a metal element other than the metal element A, but preferably contains the metal element A as the main component. The content of the metal element A (in terms of metal element) may be, for example, 50 mass% or more, preferably 70 mass% or more, more preferably 90 mass% or more, and may be 95 mass% or more, 97 mass% or more, or 99 mass% or more, or even 100 mass% based on the total amount of the supported metal.

[0036] The method for supporting the supported metal is not particularly limited, and the metal may be supported on the support by a known method, such as evaporation to dryness, pore volume method, incipient wetness method, coprecipitation method, etc.

[0037] The hydrogenation catalyst is a catalyst containing Ni. The hydrogenation catalyst may be any catalyst that can function as a catalyst for the hydrogenation reaction of acetaldol, for example.

[0038] The hydrogenation catalyst may be a known hydrogenation catalyst. For example, a Raney nickel catalyst or the like can be suitably used as the hydrogenation catalyst. Furthermore, a nickel catalyst prepared by a coprecipitation method can also be used as the hydrogenation catalyst. Furthermore, the hydrogenation catalyst is preferably a reduced and stabilized product having a Ni content of 30% by mass or more.

[0039] The Ni content (in terms of metal element) in the hydrogenation catalyst may be, for example, 20 mass% or more, 30 mass% or more, 40 mass% or more, or 50 mass% or more, based on the total amount of the hydrogenation catalyst. The Ni content (in terms of metal element) in the hydrogenation catalyst may be, for example, 90 mass% or less, 80 mass% or less, 70 mass% or less, or 60 mass% or less, based on the total amount of the hydrogenation catalyst. That is, the Ni content (converted to metal element) in the hydrogenation catalyst may be, for example, 20 to 90 mass%, 20 to 80 mass%, 20 to 70 mass%, 20 to 60 mass%, 30 to 90 mass%, 30 to 80 mass%, 30 to 70 mass%, 30 to 60 mass%, 40 to 90 mass%, 40 to 80 mass%, 40 to 70 mass%, 40 to 60 mass%, 50 to 90 mass%, 50 to 80 mass%, 50 to 70 mass%, or 50 to 60 mass%, based on the total amount of the hydrogenation catalyst.

[0040] The method for producing 1,3-butanediol according to the present embodiment is a method for obtaining 1,3-butanediol by bringing a raw material liquid containing acetaldehyde into contact with a solid base catalyst and a hydrogenation catalyst.

[0041] The raw material liquid may contain acetaldehyde and a dispersion medium. The dispersion medium may be any dispersion medium that can be uniformly mixed with acetaldehyde and that is not hydrogenated by the hydrogenation catalyst. Examples of the dispersion medium include water, ethanol, and alkanes (e.g., alkanes having 6 to 16 carbon atoms).

[0042] The raw material liquid preferably contains at least one polar solvent selected from the group consisting of ethanol and water. When the raw material liquid contains the polar solvent, the molar ratio of the polar solvent to acetaldehyde in the raw material liquid (polar solvent / acetaldehyde) may be, for example, 0.3 or more, 0.5 or more, 0.7 or more, 0.9 or more, 1 or more, 1.5 or more, or 2 or more. Furthermore, the molar ratio (polar solvent / acetaldehyde) may be, for example, 20 or less, 15 or less, 10 or less, 7 or less, or 5 or less. That is, the molar ratio of the polar solvent to acetaldehyde in the raw material liquid (polar solvent / acetaldehyde) is, for example, 0 to 20, 0 to 15, 0 to 10, 0 to 7, 0 to 5, 0.3 to 20, 0.3 to 15, 0.3 to 10, 0.3 to 7, 0.3 to 5, 0.5 to 20, 0.5 to 15, 0.5 to 10, 0.5 to 7, 0.5 to 5, 0.7 to 20 , 0.7 to 15, 0.7 to 10, 0.7 to 7, 0.7 to 5, 0.9 to 20, 0.9 to 15, 0.9 to 10, 0.9 to 7, 0.9 to 5, 1 to 20, 1 to 15, 1 to 10, 1 to 7, 1 to 5, 1.5 to 20, 1.5 to 15, 1.5 to 10, 1.5 to 7, 1.5 to 5, 2 to 20, 2 to 15, 2 to 10, 2 to 7, or 2 to 5.

[0043] It is preferable to use acetaldehyde produced by dehydrogenation of ethanol as the acetaldehyde. The ethanol may be bio-derived ethanol (bioethanol). By using bioethanol as a raw material, the obtained 1,3-butanediol is bio-derived 1,3-butanediol. The reaction liquid of the ethanol dehydrogenation reaction can be used in the production method of this embodiment as a raw material liquid containing acetaldehyde and ethanol without purification or isolation.

[0044] Furthermore, when the raw material liquid contains at least one polar solvent selected from the group consisting of ethanol and water, the polar solvent can function as a hydrogen source. When the raw material liquid contains water, the reaction selectivity improves, and the yield of 1,3-butanediol tends to be further improved. When the polar solvent contains water, the proportion of water in the polar solvent (i.e., the proportion of water to the total of water and ethanol) may be, for example, 50 mol% or more, 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, or 95 mol% or more, or even 100 mol%.

[0045] When the raw material liquid contains ethanol, the unreacted ethanol remaining after the production of 1,3-butanediol may be reused as a raw material for the production of acetaldehyde.

[0046] The content of acetaldehyde in the raw material liquid may be, for example, 5% by mass or more based on the total amount of the raw material liquid, and from the viewpoint of economic efficiency, it may be 10% by mass or more, 20% by mass or more, or 30% by mass or more. The content of acetaldehyde in the raw material liquid may be, for example, 70% by mass or less based on the total amount of the raw material liquid, and from the viewpoint of suppressing side reactions, it may be 60% by mass or less, 50% by mass or less, or 40% by mass or less. That is, the content of acetaldehyde in the raw material liquid may be, for example, 5 to 70 mass%, 5 to 60 mass%, 5 to 50 mass%, 5 to 40 mass%, 10 to 70 mass%, 10 to 60 mass%, 10 to 50 mass%, 10 to 40 mass%, 20 to 70 mass%, 20 to 60 mass%, 20 to 50 mass%, 20 to 40 mass%, 30 to 70 mass%, 30 to 60 mass%, 30 to 50 mass%, or 30 to 40 mass%, based on the total amount of the raw material liquid.

[0047] In the production method of this embodiment, it is preferable that hydrogen be present in the reaction system during the reaction in the presence of a hydrogenation catalyst.

[0048] Examples of the method for producing 1,3-butanediol according to the present embodiment include the following first embodiment (production method (1)), second embodiment (production method (2)), and third embodiment (production method (3)).

[0049] (Production Method (1)) The production method of the first aspect (production method (1)) includes a step (1-1) of contacting a raw material liquid containing acetaldehyde with a mixture of a solid base catalyst and a hydrogenation catalyst (hereinafter referred to as a catalyst mixture) to obtain a reaction liquid containing 1,3-butanediol.

[0050] In the production method (1), isolation and purification of an intermediate (for example, acetaldol) is not required, and 1,3-butanediol can be produced efficiently from a raw material solution containing acetaldehyde in a short number of steps.

[0051] In the step (1-1), the method for contacting the raw material liquid with the catalyst mixture is not particularly limited, and examples thereof include a method of supplying the raw material liquid to a batch reactor containing the catalyst mixture, and a method of passing the raw material liquid through a flow reactor containing the catalyst mixture.

[0052] The catalyst mixture may be, for example, a mixture of a particulate solid base catalyst and a particulate hydrogenation catalyst.

[0053] The proportion of the solid base catalyst in the catalyst mixture may be, for example, 30% by mass or more, 50% by mass or more, 70% by mass or more, or 90% by mass or more. The proportion of the solid base catalyst in the catalyst mixture may be, for example, 99% by mass or less, 97% by mass or less, 95% by mass or less, or 93% by mass or less. That is, the proportion of the solid base catalyst in the catalyst mixture may be, for example, 30 to 99% by mass, 30 to 97% by mass, 30 to 95% by mass, 30 to 93% by mass, 50 to 99% by mass, 50 to 97% by mass, 50 to 95% by mass, 50 to 93% by mass, 70 to 99% by mass, 70 to 97% by mass, 70 to 95% by mass, 70 to 93% by mass, 90 to 99% by mass, 90 to 97% by mass, 90 to 95% by mass, or 90 to 93% by mass.

[0054] The reaction temperature in step (1-1) (the temperature at the time of contacting the raw material liquid with the catalyst mixture) may be, for example, 0°C or higher, and from the viewpoint of further improving reactivity, it may be 30°C or higher, 40°C or higher, or 50°C or higher. Furthermore, the reaction temperature in step (1-1) may be, for example, 120°C or lower, and from the viewpoint of suppressing side reactions, it may be 100°C or lower, 80°C or lower, or 70°C or lower. That is, the reaction temperature in step (1-1) may be, for example, 0 to 120°C, 0 to 100°C, 0 to 80°C, 0 to 70°C, 30 to 120°C, 30 to 100°C, 30 to 80°C, 30 to 70°C, 40 to 120°C, 40 to 100°C, 40 to 80°C, 40 to 70°C, 50 to 120°C, 50 to 100°C, 50 to 80°C, or 50 to 70°C.

[0055] The reaction time in step (1-1) (the time during which the raw material liquid and the catalyst mixture are in contact) is not particularly limited, and may be a time during which acetaldehyde is sufficiently reacted and the intermediate acetaldol is sufficiently hydrogenated. In step (1-1), the conversion rate of acetaldehyde may be, for example, 20% or more. From the viewpoint of more efficiently obtaining 1,3-butanediol, it may be 30% or more, 50% or more, 70% or more, 80% or more, or 90% or more. In step (1-1), the reaction time may be appropriately adjusted so that the conversion rate falls within the above range.

[0056] The reaction in step (1-1) may be carried out in a batch, semi-batch or continuous manner.

[0057] When step (1-1) is performed in a batch or semi-batch manner, the amount of the catalyst mixture may be, for example, 10 parts by mass or more, 20 parts by mass or more, or 30 parts by mass or more, relative to 100 parts by mass of the raw material liquid. Furthermore, when step (1-1) is performed in a batch or semi-batch manner, the amount of the catalyst mixture may be, for example, 100 parts by mass or less, 90 parts by mass or less, 80 parts by mass or less, 70 parts by mass or less, or 60 parts by mass or less, relative to 100 parts by mass of the raw material liquid. That is, when step (1-1) is a batch process or a semi-batch process, the amount of the catalyst mixture may be, for example, 10 to 100 parts by mass, 10 to 90 parts by mass, 10 to 80 parts by mass, 10 to 70 parts by mass, 10 to 60 parts by mass, 20 to 100 parts by mass, 20 to 90 parts by mass, 20 to 80 parts by mass, 20 to 70 parts by mass, 20 to 60 parts by mass, 30 to 100 parts by mass, 30 to 90 parts by mass, 30 to 80 parts by mass, 30 to 70 parts by mass, or 30 to 60 parts by mass, relative to 100 parts by mass of the raw material liquid.

[0058] When step (1-1) is continuous, the weight hourly space velocity (WHSV) (i.e., the ratio of the feed rate of the raw material liquid to the total weight of the catalyst mixture) may be, for example, 0.01 or more, 0.05 or more, 0.1 or more, or 0.2 or more. Furthermore, when step (1-1) is continuous, the weight hourly space velocity (WHSV) may be, for example, 10 or less, 8 or less, 6 or less, or 4 or less. That is, when step (1-1) is continuous, the weight hourly space velocity (WHSV) may be, for example, 0.01 to 10, 0.01 to 8, 0.01 to 6, 0.01 to 4, 0.05 to 10, 0.05 to 8, 0.05 to 6, 0.05 to 4, 0.1 to 10, 0.1 to 8, 0.1 to 6, 0.1 to 4, 0.2 to 10, 0.2 to 8, 0.2 to 6, or 0.2 to 4.

[0059] When the step (1-1) is carried out in a batch or semi-batch manner, the step (1-1) is preferably carried out in the presence of hydrogen.

[0060] When step (1-1) is performed in a batch or semi-batch manner, the hydrogen pressure may be, for example, 0.1 MPaG or more, 0.2 MPaG or more, 0.4 MPaG or more, or 0.5 MPaG or more. When step (1-1) is performed in a batch or semi-batch manner, the hydrogen pressure may be, for example, 20 MPaG or less, 10 MPaG or less, 5 MPaG or less, or 1 MPaG or less. That is, when step (1-1) is performed in a batch or semi-batch manner, the hydrogen pressure may be, for example, 0.1 to 20 MPaG, 0.1 to 10 MPaG, 0.1 to 5 MPaG, 0.1 to 1 MPaG, 0.2 to 20 MPaG, 0.2 to 10 MPaG, 0.2 to 5 MPaG, 0.2 to 1 MPaG, 0.4 to 20 MPaG, 0.4 to 10 MPaG, 0.4 to 5 MPaG, 0.4 to 1 MPaG, 0.5 to 20 MPaG, 0.5 to 10 MPaG, 0.5 to 5 MPaG, or 0.5 to 1 MPaG.

[0061] When the step (1-1) is a continuous process, it is preferable to pass hydrogen together with the raw material liquid in the step (1-1).

[0062] When step (1-1) is performed continuously, the hydrogen pressure may be, for example, 0.1 MPaG or more, 0.5 MPaG or more, 1 MPaG or more, or 5 MPaG or more. When step (1-1) is performed continuously, the hydrogen pressure may be, for example, 50 MPaG or less, 30 MPaG or less, 20 MPaG or less, or 15 MPaG or less. That is, when step (1-1) is a continuous process, the hydrogen pressure may be, for example, 0.1 to 50 MPaG, 0.1 to 30 MPaG, 0.1 to 20 MPaG, 0.1 to 15 MPaG, 0.5 to 50 MPaG, 0.5 to 30 MPaG, 0.5 to 20 MPaG, 0.5 to 15 MPaG, 1 to 50 MPaG, 1 to 30 MPaG, 1 to 20 MPaG, 1 to 15 MPaG, 5 to 50 MPaG, 5 to 30 MPaG, 5 to 20 MPaG, or 5 to 15 MPaG.

[0063] In the step (1-1), a reaction liquid containing 1,3-butanediol is obtained.

[0064] The reaction liquid may further contain a dispersion medium. The reaction liquid may further contain acetaldehyde. The dispersion medium and acetaldehyde contained in the reaction liquid may be reused as the raw material liquid.

[0065] The reaction liquid may further contain ethanol. When the reaction liquid contains ethanol, the ethanol may be reused as a raw material for producing acetaldehyde.

[0066] The production method (1) may further include a step of isolating and purifying 1,3-butanediol from the reaction solution. The method for isolating and purifying 1,3-butanediol is not particularly limited, and may be selected from known isolation and purification methods without particular limitation.

[0067] (Production Method (2)) The production method of the second embodiment (Production Method (2)) includes a first step (step (2-1)) of contacting a raw material liquid containing acetaldehyde with a solid base catalyst to obtain a mixed liquid containing acetaldol, and a second step (step (2-2)) of contacting the mixed liquid obtained in the first step with a hydrogenation catalyst to obtain a reaction liquid containing 1,3-butanediol.

[0068] In the production method (2), acetaldol is not isolated or purified from the mixture obtained in the first step, and the mixture is directly subjected to the second step, thereby enabling efficient production of 1,3-butanediol in a short number of steps.

[0069] It is preferable that the step (2-1) and the step (2-2) are carried out in separate reactors.

[0070] Step (2-1) is a step of carrying out an aldol reaction of acetaldehyde in the presence of a solid base catalyst to produce acetaldol.

[0071] In the step (2-1), the method for contacting the raw material liquid with the solid base catalyst is not particularly limited, and examples thereof include a method of supplying the raw material liquid to a batch reactor containing the solid base catalyst, and a method of passing the raw material liquid through a flow reactor containing the solid base catalyst.

[0072] The reaction temperature in step (2-1) (the temperature at the time of contacting the raw material liquid with the solid base catalyst) may be, for example, 0°C or higher, and from the viewpoint of further improving reactivity, it may be 30°C or higher, 40°C or higher, or 50°C or higher. Furthermore, the reaction temperature in step (2-1) may be, for example, 120°C or lower, and from the viewpoint of suppressing side reactions, it may be 100°C or lower, 80°C or lower, or 70°C or lower. That is, the reaction temperature in step (2-1) may be, for example, 0 to 120°C, 0 to 100°C, 0 to 80°C, 0 to 70°C, 30 to 120°C, 30 to 100°C, 30 to 80°C, 30 to 70°C, 40 to 120°C, 40 to 100°C, 40 to 80°C, 40 to 70°C, 50 to 120°C, 50 to 100°C, 50 to 80°C, or 50 to 70°C.

[0073] The reaction time in step (2-1) (the time during which the raw material liquid and the solid base catalyst are in contact) is not particularly limited, and may be a time that allows acetaldehyde to react sufficiently. In step (2-1), the conversion rate of acetaldehyde may be, for example, 20% or more, and from the viewpoint of more efficiently obtaining 1,3-butanediol, it may be 30% or more, 50% or more, 70% or more, 80% or more, 90% or more, or 99% or more. In step (2-1), the reaction time may be appropriately adjusted so that the conversion rate falls within the above range.

[0074] The reaction in step (2-1) may be carried out in a batch, semi-batch or continuous manner.

[0075] When step (2-1) is performed in a batch or semi-batch manner, the amount of the solid base catalyst may be, for example, 10 parts by mass or more, 20 parts by mass or more, or 30 parts by mass or more, relative to 100 parts by mass of the raw material liquid. Furthermore, when step (2-1) is performed in a batch or semi-batch manner, the amount of the solid base catalyst may be, for example, 100 parts by mass or less, 80 parts by mass or less, 60 parts by mass or less, or 50 parts by mass or less, relative to 100 parts by mass of the raw material liquid. That is, when step (2-1) is performed in a batch or semi-batch system, the amount of the solid base catalyst may be, for example, 10 to 100 parts by mass, 10 to 80 parts by mass, 10 to 60 parts by mass, 10 to 50 parts by mass, 20 to 100 parts by mass, 20 to 80 parts by mass, 20 to 60 parts by mass, 20 to 50 parts by mass, 30 to 100 parts by mass, 30 to 80 parts by mass, 30 to 60 parts by mass, or 30 to 50 parts by mass, relative to 100 parts by mass of the raw material liquid.

[0076] When step (2-1) is performed continuously, the weight hourly space velocity (WHSV) (i.e., the ratio of the feed rate of the raw material liquid to the weight of the solid base catalyst) may be, for example, 0.01 or more, 0.05 or more, or 0.1 or more. When step (2-1) is performed continuously, the weight hourly space velocity (WHSV) may be, for example, 5 or less, 3 or less, 1 or less, or 0.5 or less. That is, when step (2-1) is performed continuously, the weight hourly space velocity (WHSV) may be, for example, 0.01 to 5, 0.01 to 3, 0.01 to 1, 0.01 to 0.5, 0.05 to 5, 0.05 to 3, 0.05 to 1, 0.05 to 0.5, 0.1 to 5, 0.1 to 3, 0.1 to 1, or 0.1 to 0.5.

[0077] In step (2-1), a mixed liquid containing acetaldol is obtained. The mixed liquid may further contain components other than acetaldol. For example, the mixed liquid may further contain unreacted acetaldehyde. Furthermore, the mixed liquid may further contain components contained in the raw material liquid, such as a dispersion medium.

[0078] The mixture obtained in the step (2-1) is subjected to the step (2-2) without isolation, purification, etc.

[0079] The step (2-2) is a step of contacting the mixed liquid obtained in the step (2-1) with a hydrogenation catalyst to obtain a reaction liquid containing 1,3-butanediol.

[0080] In the step (2-2), the method for contacting the mixed liquid with the hydrogenation catalyst is not particularly limited, and examples thereof include a method of supplying the mixed liquid to a batch reactor containing a hydrogenation catalyst, and a method of passing the mixed liquid through a flow reactor containing a hydrogenation catalyst.

[0081] The reaction temperature in step (2-2) (the temperature at the time of contacting the mixed solution with the hydrogenation catalyst) may be, for example, 0° C. or higher, and from the viewpoint of further improving reactivity, may be 30° C. or higher, 40° C. or higher, or 45° C. or higher. The reaction temperature in step (2-2) may be, for example, 150° C. or lower, and from the viewpoint of suppressing side reactions, may be 110° C. or lower, 100° C. or lower, 90° C. or lower, or 80° C. or lower. That is, the reaction temperature in step (2-2) may be, for example, 0 to 150°C, 0 to 110°C, 0 to 100°C, 0 to 90°C, 0 to 80°C, 30 to 150°C, 30 to 110°C, 30 to 100°C, 30 to 90°C, 30 to 80°C, 40 to 150°C, 40 to 110°C, 40 to 100°C, 40 to 90°C, 40 to 80°C, 45 to 150°C, 45 to 110°C, 45 to 100°C, 45 to 90°C, or 45 to 80°C.

[0082] The reaction time in step (2-2) (the time during which the mixed solution is in contact with the hydrogenation catalyst) is not particularly limited as long as it is a time during which acetaldol is sufficiently hydrogenated. In step (2-2), the conversion rate of acetaldol may be, for example, 50% or more. From the viewpoint of more efficiently obtaining 1,3-butanediol, it may be 60% or more, 70% or more, 80% or more, or 90% or more. In step (2-2), the reaction time may be appropriately adjusted so that the conversion rate falls within the above range.

[0083] The reaction in step (2-2) may be carried out batchwise, semi-batchwise or continuously.

[0084] When step (2-2) is performed in a batch or semi-batch manner, the amount of the hydrogenation catalyst may be, for example, 10 parts by mass or more, 20 parts by mass or more, or 30 parts by mass or more, relative to 100 parts by mass of the mixed liquid. Furthermore, when step (2-2) is performed in a batch or semi-batch manner, the amount of the hydrogenation catalyst may be, for example, 100 parts by mass or less, 80 parts by mass or less, 70 parts by mass or less, or 60 parts by mass or less, relative to 100 parts by mass of the mixed liquid. That is, when step (2-2) is performed batchwise or semi-batchwise, the amount of the hydrogenation catalyst may be, for example, 10 to 100 parts by mass, 10 to 80 parts by mass, 10 to 70 parts by mass, 10 to 60 parts by mass, 20 to 100 parts by mass, 20 to 80 parts by mass, 20 to 70 parts by mass, 20 to 60 parts by mass, 30 to 100 parts by mass, 30 to 80 parts by mass, 30 to 70 parts by mass, or 30 to 60 parts by mass, relative to 100 parts by mass of the mixed liquid.

[0085] When the step (2-2) is performed continuously, the weight hourly space velocity (WHSV) (i.e., the ratio of the supply rate of the mixed liquid to the weight of the hydrogenation catalyst) may be, for example, 0.01 or more, 0.05 or more, or 0.1 or more. When the step (2-1) is performed continuously, the weight hourly space velocity (WHSV) may be, for example, 5 or less, 3 or less, 1 or less, or 0.5 or less. That is, when the step (2-1) is performed continuously, the weight hourly space velocity (WHSV) may be, for example, 0.01 to 5, 0.01 to 3, 0.01 to 1, 0.01 to 0.5, 0.05 to 5, 0.05 to 3, 0.05 to 1, 0.05 to 0.5, 0.1 to 5, 0.1 to 3, 0.1 to 1, or 0.1 to 0.5.

[0086] When the step (2-2) is carried out in a batch or semi-batch manner, the step (2-2) is preferably carried out in the presence of hydrogen.

[0087] When step (2-1) is performed in a batch or semi-batch manner, the hydrogen pressure may be, for example, 0.1 MPaG or more, 0.3 MPaG or more, 0.4 MPaG or more, or 0.5 MPaG or more. When step (2-1) is performed in a batch or semi-batch manner, the hydrogen pressure may be, for example, 50 MPaG or less, 40 MPaG or less, 30 MPaG or less, or 20 MPaG or less. That is, when step (2-1) is performed in a batch or semi-batch manner, the hydrogen pressure may be, for example, 0.1 to 50 MPaG, 0.1 to 40 MPaG, 0.1 to 30 MPaG, 0.1 to 20 MPaG, 0.3 to 50 MPaG, 0.3 to 40 MPaG, 0.3 to 30 MPaG, 0.3 to 20 MPaG, 0.4 to 50 MPaG, 0.4 to 40 MPaG, 0.4 to 30 MPaG, 0.4 to 20 MPaG, 0.5 to 50 MPaG, 0.5 to 40 MPaG, 0.5 to 30 MPaG, or 0.5 to 20 MPaG.

[0088] When the step (2-2) is a continuous process, it is preferable to pass hydrogen together with the raw material liquid in the step (1-1).

[0089] When step (2-1) is performed continuously, the hydrogen pressure may be, for example, 0.1 MPaG or more, 0.3 MPaG or more, 0.4 MPaG or more, or 0.5 MPaG or more. When step (2-1) is performed continuously, the hydrogen pressure may be, for example, 50 MPaG or less, 40 MPaG or less, 30 MPaG or less, or 20 MPaG or less. That is, when step (2-1) is a continuous process, the hydrogen pressure may be, for example, 0.1 to 50 MPaG, 0.1 to 40 MPaG, 0.1 to 30 MPaG, 0.1 to 20 MPaG, 0.3 to 50 MPaG, 0.3 to 40 MPaG, 0.3 to 30 MPaG, 0.3 to 20 MPaG, 0.4 to 50 MPaG, 0.4 to 40 MPaG, 0.4 to 30 MPaG, 0.4 to 20 MPaG, 0.5 to 50 MPaG, 0.5 to 40 MPaG, 0.5 to 30 MPaG, or 0.5 to 20 MPaG.

[0090] In the step (2-2), a reaction liquid containing 1,3-butanediol is obtained.

[0091] The reaction liquid may further contain a dispersion medium. The reaction liquid may further contain acetaldehyde. The dispersion medium and acetaldehyde contained in the reaction liquid may be reused as the raw material liquid.

[0092] The reaction liquid may further contain ethanol. When the reaction liquid contains ethanol, the ethanol may be reused as a raw material for producing acetaldehyde.

[0093] The production method (2) may further include a step of isolating and purifying 1,3-butanediol from the reaction solution. The method for isolating and purifying 1,3-butanediol is not particularly limited, and may be selected from known isolation and purification methods without particular limitation.

[0094] (Production Method (3)) The production method of the third aspect (production method (3)) includes a step (3-1) of circulating a raw material liquid containing acetaldehyde through a reactor equipped with a first catalyst layer containing a solid base catalyst and a second catalyst layer containing a hydrogenation catalyst to obtain a reaction liquid containing 1,3-butanediol.

[0095] In the production method (3), the raw material liquid is brought into contact with a first catalyst layer and then with a second catalyst layer, thereby producing 1,3-butanediol from acetaldehyde in one step.

[0096] The first catalyst layer contains a solid base catalyst. The shape of the solid base catalyst in the first catalyst layer is not particularly limited, and may be, for example, granular, powdery, honeycomb, or the like.

[0097] The second catalyst layer contains a hydrogenation catalyst. The shape of the hydrogenation catalyst in the second catalyst layer is not particularly limited, and may be, for example, granular, powdery, honeycomb, or the like.

[0098] The reaction temperature in the first catalyst layer may be, for example, 0°C or higher, and from the viewpoint of further improving reactivity, it may be 30°C or higher, 40°C or higher, or 50°C or higher. Furthermore, the reaction temperature in the first catalyst layer may be, for example, 120°C or lower, and from the viewpoint of suppressing side reactions, it may be 100°C or lower, 80°C or lower, or 70°C or lower. That is, the reaction temperature in the first catalyst layer may be, for example, 0 to 120°C, 0 to 100°C, 0 to 80°C, 0 to 70°C, 30 to 120°C, 30 to 100°C, 30 to 80°C, 30 to 70°C, 40 to 120°C, 40 to 100°C, 40 to 80°C, 40 to 70°C, 50 to 120°C, 50 to 100°C, 50 to 80°C, or 50 to 70°C.

[0099] The reaction temperature in the second catalyst layer may be, for example, 0° C. or higher, and from the viewpoint of further improving reactivity, may be 30° C. or higher, a temperature exceeding 40° C., 43° C. or higher, 45° C. or higher, or 50° C. or higher. The reaction temperature in the second catalyst layer may be, for example, 150° C. or lower, and from the viewpoint of suppressing side reactions, may be 120° C. or lower, 100° C. or lower, 90° C. or lower, 80° C. or lower, or 70° C. or lower. That is, the reaction temperature in the second catalyst layer may be, for example, 0 to 150°C, 0 to 120°C, 0 to 100°C, 0 to 80°C, 0 to 70°C, 30 to 120°C, 30 to 100°C, 30 to 80°C, 30 to 70°C, greater than 40°C to 150°C, greater than 40°C to 120°C, greater than 40°C to 100°C, greater than 40°C to 80°C, greater than 40°C to 70°C, 43 to 150°C, 43 to 120°C, 43 to 100°C, 43 to 80°C, 43 to 70°C, 45 to 150°C, 45 to 120°C, 45 to 100°C, 45 to 80°C, 45 to 70°C, 50 to 150°C, 50 to 120°C, 50 to 100°C, 50 to 80°C, or 50 to 70°C.

[0100] The weight hourly space velocity (WHSV) for the first catalyst layer (i.e., the ratio of the acetaldehyde supply rate to the weight of the solid base catalyst) may be, for example, 0.01 or more, 0.05 or more, 0.1 or more, or 0.2 or more. The weight hourly space velocity (WHSV) for the first catalyst layer (i.e., the ratio of the acetaldehyde supply rate to the weight of the solid base catalyst) may be, for example, 5 or less, 3 or less, 1 or less, or 0.5 or less. That is, the weight hourly space velocity (WHSV) for the first catalyst layer may be, for example, 0.01 to 5, 0.01 to 3, 0.01 to 1, 0.01 to 0.5, 0.05 to 5, 0.05 to 3, 0.05 to 1, 0.05 to 0.5, 0.1 to 5, 0.1 to 3, 0.1 to 1, 0.1 to 0.5, 0.2 to 5, 0.2 to 3, 0.2 to 1, or 0.2 to 0.5.

[0101] The weight hourly space velocity (WHSV) for the second catalyst layer (i.e., the ratio of the supply rate of acetaldehyde to the weight of the hydrogenation catalyst) may be, for example, 0.01 or more, 0.05 or more, 0.1 or more, or 0.2 or more. The weight hourly space velocity (WHSV) for the second catalyst layer (i.e., the ratio of the supply rate of acetaldehyde to the weight of the hydrogenation catalyst) may be, for example, 5 or less, 3 or less, 1 or less, or 0.5 or less. That is, the weight hourly space velocity (WHSV) for the second catalyst layer may be, for example, 0.01 to 5, 0.01 to 3, 0.01 to 1, 0.01 to 0.5, 0.05 to 5, 0.05 to 3, 0.05 to 1, 0.05 to 0.5, 0.1 to 5, 0.1 to 3, 0.1 to 1, 0.1 to 0.5, 0.2 to 5, 0.2 to 3, 0.2 to 1, or 0.2 to 0.5.

[0102] In the step (3-1), it is preferable to pass hydrogen along with the raw material liquid.

[0103] The hydrogen pressure in step (3-1) may be, for example, 0.01 MPaG or more, 0.1 MPaG or more, 0.2 MPaG or more, or 0.3 MPaG or more. The hydrogen pressure in step (3-1) may be, for example, 30 MPaG or less, 20 MPaG or less, 10 MPaG or less, or 5 MPaG or less. That is, the hydrogen pressure in step (3-1) may be, for example, 0.01 to 30 MPaG, 0.01 to 20 MPaG, 0.01 to 10 MPaG, 0.01 to 5 MPaG, 0.1 to 30 MPaG, 0.1 to 20 MPaG, 0.1 to 10 MPaG, 0.1 to 5 MPaG, 0.2 to 30 MPaG, 0.2 to 20 MPaG, 0.2 to 10 MPaG, 0.2 to 5 MPaG, 0.3 to 30 MPaG, 0.3 to 20 MPaG, 0.3 to 10 MPaG, or 0.3 to 5 MPaG.

[0104] In the step (3-1), a reaction liquid containing 1,3-butanediol is obtained.

[0105] The reaction liquid may further contain a dispersion medium. The reaction liquid may further contain acetaldehyde. The dispersion medium and acetaldehyde contained in the reaction liquid may be reused as the raw material liquid.

[0106] The reaction liquid may further contain ethanol. When the reaction liquid contains ethanol, the ethanol may be reused as a raw material for producing acetaldehyde.

[0107] The production method (3) may further include a step of isolating and purifying 1,3-butanediol from the reaction solution. The method for isolating and purifying 1,3-butanediol is not particularly limited, and may be selected from known isolation and purification methods without particular limitation.

[0108] Although the preferred embodiments of the present disclosure have been described above, the present disclosure is not limited to the above embodiments.

[0109] The present disclosure will be described in more detail below with reference to examples, but the present disclosure is not limited to these examples.

[0110] (Example 1-1) (1) Preparation of solid base catalyst 1-1. As a support, spherical silica, CARIACT Q6 (specific surface area: 400 m), manufactured by Fuji Silysia Chemical Co., Ltd. ２ / g) was used. Magnesium nitrate was dissolved in water as a precursor of the active metal, and the carrier was impregnated with the solution so that the amount of the active metal supported was 5 mass %. After the support, the catalyst was dried at 130°C and then calcined at 500°C for 3 hours to obtain solid base catalyst 1-1.

[0111] (2) Production of 1,3-butanediol A commercially available hydrogenation catalyst, N108F (Ni content: 52% by mass) (reduced and stabilized product) manufactured by JGC Catalysts and Chemicals, was prepared. A 30 mL autoclave manufactured by Taiatsu Glass Industries Co., Ltd. was filled with a mixture of 0.40 g of solid acid catalyst 1-1 and 0.04 g of a hydrogenation catalyst. A small-grain stirrer and 1.2 g of a mixture of ethanol and acetaldehyde (ethanol / acetaldehyde = 3 mol / mol) were then added. The atmosphere inside the autoclave was purged with hydrogen and then filled with hydrogen to a hydrogen pressure of 0.55 MPaG at room temperature. The autoclave was placed in an oil bath at 60°C and reacted for 4 hours with stirring. The reaction liquid was collected with a dropper, filtered through a 0.7 μm pore size filter, and the composition was analyzed by gas chromatography.

[0112] (3) Evaluation of Reaction From the results of the composition analysis in (2) above, the acetaldehyde conversion rate (%) and the 1,3-butanediol yield (%) were calculated by the following method. The results are shown in Table 1. Acetaldehyde conversion rate (%) = 100 - (acetaldehyde concentration in reaction solution - acetaldehyde concentration before reaction) x 100 1,3-butanediol yield (%) = (1,3-butanediol concentration in reaction solution / acetaldehyde concentration before reaction) x 100

[0113] (Example 1-2) (1) Preparation of solid base catalyst 1-2. As a support, spherical silica (CARIACT Q6, specific surface area 400 m) manufactured by Fuji Silysia Chemical Co., Ltd. was used. ２ / g). Potassium nitrate was dissolved in water as a precursor of the active metal, and the carrier was impregnated with the active metal so that the amount of the supported active metal was 5 mass %. After the support, the support was dried at 130°C and then calcined at 500°C for 3 hours to obtain solid base catalyst 1-2.

[0114] (2) Production of 1,3-butanediol 1,3-butanediol was produced and evaluated in the same manner as in Example 1-1, except that solid base catalyst 1-2 was used instead of solid base catalyst 1-1. The results are shown in Table 1.

[0115] (Example 1-3) (1) Preparation of solid base catalyst 1-3 As a support, spherical silica (CARIACT Q6, specific surface area 400 m) manufactured by Fuji Silysia Chemical Co., Ltd. ２ Calcium nitrate was dissolved in water as a precursor of the active metal, and the catalyst was impregnated and loaded with the active metal in an amount of 5 mass %. After loading, the catalyst was dried at 130°C and then calcined at 650°C for 3 hours to obtain solid base catalyst 1-3.

[0116] (2) Production of 1,3-butanediol 1,3-butanediol was produced and evaluated in the same manner as in Example 1-1, except that solid base catalyst 1-3 was used instead of solid base catalyst 1-1. The results are shown in Table 1.

[0117] (Comparative Examples 1-1 to 1-12) (1) Preparation of Solid Base Catalysts 1-4 to 1-15 Solid base catalysts were prepared by the following method. (i) Catalyst 1-4: Carriact Q6 (specific surface area 400 m), which is spherical silica manufactured by Fuji Silysia Chemical Co., Ltd., was used as a carrier. ２ / g). Cesium nitrate was dissolved in water as a precursor of the active metal, and the carrier was impregnated with the active metal so that the amount of the supported active metal was 5 mass %. After the support, the support was dried at 130°C and then calcined at 650°C for 3 hours to obtain solid base catalyst 1-4.

[0118] (ii) Catalyst 1-5: Carriact Q6 (specific surface area 400 m), a spherical silica material manufactured by Fuji Silysia Chemical Co., Ltd., was used as a carrier. ２ / g). Barium nitrate was dissolved in water as a precursor of the active metal, and the carrier was impregnated with the active metal so that the amount of the supported active metal was 3 mass %. After the support, the support was dried at 130°C and then calcined at 650°C for 3 hours to obtain solid base catalyst 1-5.

[0119] (iii) Catalyst 1-6: Carriact Q6 (specific surface area 400 m), a spherical silica material manufactured by Fuji Silysia Chemical Co., Ltd., was used as a carrier. ２ / g). Zinc nitrate was dissolved in water as a precursor of the active metal, and the carrier was impregnated with the active metal so that the amount of the supported active metal was 5 mass %. After the support, the support was dried at 130°C and then calcined at 500°C for 3 hours to obtain solid base catalyst 1-6.

[0120] (iv) Catalyst 1-7: Carriact Q6 (specific surface area 400 m), a spherical silica material manufactured by Fuji Silysia Chemical Co., Ltd., was used as a carrier. ２ / g). Zirconyl nitrate was dissolved in water as a precursor of the active metal, and the carrier was impregnated with the active metal so that the amount of the supported active metal was 5 mass %. After the support, the support was dried at 130°C and then calcined at 500°C for 3 hours to obtain solid base catalyst 1-7.

[0121] (v) Catalyst 1-8: Carriact Q6 (specific surface area 400 m), a spherical silica material manufactured by Fuji Silysia Chemical Co., Ltd., was used as a carrier. ２ / g). Tantalum ethoxide was dissolved in ethanol as a precursor of the active metal, and the carrier was impregnated with the solution so that the amount of the active metal supported was 5 mass %. After the support was completed, the catalyst was dried at 130°C and then calcined at 500°C for 3 hours to obtain solid base catalyst 1-8.

[0122] (vi) Catalyst 1-9: Carriact Q6 (specific surface area 400 m), a spherical silica manufactured by Fuji Silysia Chemical Co., Ltd., was used as a carrier. ２ / g). Hafnium chloride was dissolved in water as a precursor of the active metal, and the carrier was impregnated with the active metal so that the amount of the supported active metal was 5 mass %. After the support, the support was dried at 130°C and then calcined at 500°C for 3 hours to obtain solid base catalyst 1-9.

[0123] (vii) Catalyst 1-10: Carriact Q6 (specific surface area 400 m), which is spherical silica manufactured by Fuji Silysia Chemical Co., Ltd., was used as a carrier. ２ / g). Hexaammonium heptamolybdate was dissolved in water as a precursor of the active metal, and the carrier was impregnated with the solution so that the amount of the active metal supported was 5 mass %. After the support was completed, the catalyst was dried at 130°C and then calcined at 500°C for 3 hours to obtain solid base catalyst 1-10.

[0124] (viii) Catalyst 1-11: Carriact Q6 (specific surface area 400 m), which is spherical silica manufactured by Fuji Silysia Chemical Co., Ltd., was used as a carrier. ２ / g). Cerium nitrate was dissolved in water as a precursor of the active metal, and the carrier was impregnated with the solution so that the amount of the active metal supported was 5 mass %. After the support was completed, the catalyst was dried at 130°C and then calcined at 400°C for 3 hours to obtain solid base catalyst 1-11.

[0125] (ix) Catalyst 1-12: Carriact Q6 (specific surface area 400 m), a spherical silica material manufactured by Fuji Silysia Chemical Co., Ltd., was used as a carrier. ２ / g) was used. Ammonium vanadate was dissolved in water as a precursor of the active metal, and the carrier was impregnated with the solution so that the amount of the active metal supported was 5 mass %. After the support was completed, the catalyst was dried at 130°C and then calcined at 400°C for 3 hours to obtain solid base catalyst 1-12.

[0126] (x) Catalyst 1-13: Carriact Q6 (specific surface area 400 m), a spherical silica material manufactured by Fuji Silysia Chemical Co., Ltd., was used as a carrier. ２ Nickel nitrate was dissolved in water as a precursor of the active metal, and the carrier was impregnated with the solution so that the amount of the active metal supported was 5 mass %. After the support was completed, the catalyst was dried at 130°C and then calcined at 350°C for 3 hours to obtain solid base catalyst 1-13.

[0127] (xi) Catalyst 1-14: Cariact Q6 (specific surface area: 400 m / g), a spherical silica manufactured by Fuji Silysia Chemical Co., Ltd., was used as the support. Cobalt nitrate was dissolved in water as an active metal precursor, and the support was impregnated with the active metal so that the amount of the supported active metal was 5% by mass. After the support, the support was dried at 130°C and then calcined at 350°C for 3 hours to obtain solid base catalyst 1-14.

[0128] (xii) Catalyst 1-15: Carriact Q6 (specific surface area 400 m), a spherical silica material manufactured by Fuji Silysia Chemical Co., Ltd., was used as a carrier. ２ / g). Iron nitrate was dissolved in water as a precursor of the active metal, and the carrier was impregnated with the active metal so that the amount of the supported active metal was 5 mass %. After the support, the support was dried at 130°C and then calcined at 350°C for 3 hours to obtain solid base catalyst 1-15.

[0129] (2) Production of 1,3-butanediol 1,3-butanediol was produced and evaluated in the same manner as in Example 1-1, except that catalysts 1-4 to 1-15 were used instead of solid base catalyst 1-1. The results are shown in Table 1.

[0130]

[0131] (Example 2-1) (1) Preparation of solid base catalyst 2-1 γ-alumina (specific surface area: 180 m) manufactured by Mizusawa Chemical Industries, Ltd. was used as a carrier. ２ A solid base catalyst was prepared in the same manner as in Example 1-1, except that solid base catalyst 2-1 was used instead of solid base catalyst 1-1, to obtain solid base catalyst 2-1. (2) Production of 1,3-butanediol 1,3-butanediol was produced and evaluated in the same manner as in Example 1-1, except that solid base catalyst 2-1 was used instead of solid base catalyst 1-1. The results are shown in Table 2.

[0132] (Example 2-2) (1) Preparation of solid base catalyst 2-2 γ-alumina (specific surface area: 280 m) manufactured by Sumitomo Chemical Co., Ltd. was used as a carrier. ２ A solid base catalyst was prepared in the same manner as in Example 1-1, except that solid base catalyst 2-2 was used instead of solid base catalyst 1-1, to obtain solid base catalyst 2-2. (2) Production of 1,3-butanediol 1,3-butanediol was produced and evaluated in the same manner as in Example 1-1, except that solid base catalyst 2-2 was used instead of solid base catalyst 1-1. The results are shown in Table 2.

[0133] (Example 2-3) (1) Preparation of Solid Base Catalyst 2-3 A solid base catalyst was prepared in the same manner as in Example 1-1, except that magnesia alumina was used as the support, to obtain Solid Base Catalyst 2-3. (2) Production of 1,3-Butanediol 1,3-butanediol was produced and evaluated in the same manner as in Example 1-1, except that Solid Base Catalyst 2-3 was used instead of Solid Base Catalyst 1-1. The results are shown in Table 2.

[0134] The magnesia-alumina used in the examples was all produced by the following method.

[0135] (Production of Magnesia Alumina) 20.0 g of commercially available γ-alumina (manufactured by Mizusawa Chemical Industries) was mixed with an aqueous solution prepared by dissolving 25.1 g of magnesium nitrate hexahydrate (manufactured by Wako Pure Chemical Industries) in water (approximately 150 ml), and the water was removed using an evaporator at approximately 50°C. The mixture was then dried overnight at 130°C, calcined for 3 hours at 550°C, and subsequently calcined for 3 hours at 800°C. The resulting calcined product was mixed with an aqueous solution prepared by dissolving 25.1 g of magnesium nitrate hexahydrate (manufactured by Wako Pure Chemical Industries) in water (approximately 150 ml), and the water was removed using an evaporator at approximately 50°C. The mixture was then dried overnight at 130°C, calcined for 3 hours at 550°C, and subsequently calcined for 3 hours at 800°C. As a result, magnesium alumina having a spinel structure was obtained. In addition, X-ray diffraction measurement of the obtained magnesia alumina confirmed that diffraction peaks derived from Mg spinel were observed at 2θ=36.9, 44.8, 59.4, and 65.3 deg.

[0136]

[0137] (Example 3-1) (1) Production of 1,3-butanediol Instead of the solid base catalyst 1-1, γ-alumina (specific surface area: 180 m) manufactured by Mizusawa Chemical Industries, Ltd. ２ The results are shown in Table 3.

[0138] (Example 3-2) (1) Production of 1,3-butanediol Instead of the solid base catalyst 1-1, γ-alumina (specific surface area: 280 m) manufactured by Sumitomo Chemical Co., Ltd. ２ The results are shown in Table 3.

[0139] (Example 3-3) (1) Production of 1,3-butanediol Instead of the solid base catalyst 1-1, magnesia (specific surface area: 40 m) manufactured by Kanto Chemical Co., Inc. was used. ２ The results are shown in Table 3.

[0140] (Example 3-4) (1) Production of 1,3-butanediol 1,3-butanediol was produced and evaluated in the same manner as in Example 1-1, except that magnesia alumina was used instead of solid base catalyst 1-1. The results are shown in Table 3.

[0141] (Comparative Example 3-1) (1) Production of 1,3-butanediol Instead of the solid base catalyst 1-1, spherical silica, CARIACT Q6 (specific surface area: 400 m), manufactured by Fuji Silysia Chemical ２ The results are shown in Table 3.

[0142]

[0143] (Example 4-1) (1) Production of 1,3-butanediol 1,3-butanediol was produced and evaluated in the same manner as in Example 1-1, except that the molar ratio of ethanol to acetaldehyde (ethanol / acetaldehyde) was set to 1. The results are shown in Table 4.

[0144] (Example 4-2) (1) Production of 1,3-butanediol 1,3-butanediol was produced and evaluated in the same manner as in Example 1-1, except that the molar ratio of ethanol to acetaldehyde (ethanol / acetaldehyde) was set to 6. The results are shown in Table 4.

[0145]

[0146] (Example 5-1) (1) Preparation of solid base catalyst 5-1 A solid base catalyst was prepared in the same manner as in Example 1-1, except that the amount of supported active metal was changed to 11 mass%, to obtain solid base catalyst 5-1. (2) Production of 1,3-butanediol 1,3-butanediol was produced and evaluated in the same manner as in Example 1-1, except that solid base catalyst 5-1 was used instead of solid base catalyst 1-1. The results are shown in Table 5.

[0147] (Example 5-2) (1) Preparation of solid base catalyst 5-2 A solid base catalyst was prepared in the same manner as in Example 1-1, except that the amount of supported active metal was changed to 3 mass%, to obtain solid base catalyst 5-2. (2) Production of 1,3-butanediol 1,3-butanediol was produced and evaluated in the same manner as in Example 1-1, except that solid base catalyst 5-2 was used instead of solid base catalyst 1-1. The results are shown in Table 5.

[0148]

[0149] (Example 6-1) (1) Production of 1,3-butanediol 1,3-butanediol was produced and evaluated in the same manner as in Example 1-1, except that the reaction temperature was changed from 60°C to 50°C, the amount of hydrogenation catalyst used was 0.12 g, and the reaction time was changed to 6 hours. The results are shown in Table 6.

[0150] (Example 6-2) (1) Production of 1,3-butanediol 1,3-butanediol was produced and evaluated in the same manner as in Example 1-1, except that the reaction temperature was changed from 60°C to 80°C and the amount of hydrogenation catalyst used was changed to 0.12 g. The results are shown in Table 6.

[0151] (Example 7-1) (1) Production of 1,3-butanediol 1,3-butanediol was produced and evaluated in the same manner as in Example 1-1, except that magnesia alumina was used instead of solid base catalyst 1-1, the reaction temperature was changed from 60°C to 40°C, and the amount of hydrogenation catalyst used was changed to 0.2 g. The results are shown in Table 7.

[0152] (Example 7-2) (1) Production of 1,3-butanediol Production and evaluation of 1,3-butanediol were carried out in the same manner as in Example 7-1, except that the reaction temperature was changed to 50° C. The results are shown in Table 7.

[0153] (Example 7-3) (1) Production of 1,3-butanediol 1,3-butanediol was produced and evaluated in the same manner as in Example 7-1, except that the reaction temperature was changed to 60° C. The results are shown in Table 7.

[0154]

[0155] Examples 8-1 to 8-14 (1) Apparatus Configuration A flow reactor in which a first reactor and a second reactor were connected was prepared. The first reactor (front stage) was packed with 33 g of the solid base catalyst 2-3 of Example 2-3, and the second reactor (rear stage) was packed with 59 g of the same hydrogenation catalyst as used in Example 1-1. (2) Production of 1,3-Butanediol 1,3-butanediol was produced using a mixture of ethanol and acetaldehyde as the raw material liquid, with the reaction temperature (°C) of the first reactor, the reaction temperature (°C) of the second reactor, the hydrogen pressure (MPaG), the flow rate of the raw material liquid (mL / h), and the ratio of ethanol to acetaldehyde in the raw material liquid (EtOH / AcH) set as shown in Table 8. The acetaldehyde conversion (conversion rate (%)) and 1,3-butanediol yield (yield (%)) were determined. The results are shown in Table 8.

[0156]

[0157] Examples 9-1 to 9-4 (1) Apparatus Configuration A flow reactor equipped with a stacked reactor was prepared. The front section of the reactor was packed with the solid base catalyst 2-3 of Example 2-3, and the rear section was packed with the same hydrogenation catalyst as the hydrogenation catalyst used in Example 1-1. The amount of each catalyst packed was as shown in Table 9. (2) Production of 1,3-butanediol 1,3-butanediol was produced using a mixture of ethanol and acetaldehyde (ethanol / acetaldehyde = 3 mol / mol) as the raw material liquid, with the reactor temperature (°C), hydrogen pressure (MPaG), and WHSV (1 / h) as shown in Table 9, and the acetaldehyde conversion (conversion (%)) and 1,3-butanediol yield (yield (%)) were determined. The results are shown in Table 9.

[0158] Example 9-5 1,3-butanediol was produced in the same manner as in Example 9-5, except that the catalyst in the first stage was changed to magnesia alumina. The results are shown in Table 9.

[0159]

[0160] Example 10-1 Instead of the solid base catalyst 1-1, magnesia (specific surface area 40 m) manufactured by Kanto Chemical Co., Ltd. ２1,3-Butanediol was produced and evaluated in the same manner as in Example 1-1, except that the solid base catalyst used in Example 3-3 was used, the raw material liquid was a mixture of acetaldehyde, ethanol, and water (acetaldehyde / ethanol / water=50 / 25 / 25 (mass ratio)), and the reaction conditions were 60°C and 7 hours. The results are shown in Table 10.

[0161] Example 10-2 1,3-butanediol was produced and evaluated in the same manner as in Example 10-1, except that the reaction conditions were changed to 4 hours at 25° C. and 3 hours at 60° C. The results are shown in Table 10.

[0162] Example 10-3 1,3-butanediol was produced and evaluated in the same manner as in Example 10-1, except that the raw material liquid was a mixture of acetaldehyde and water (acetaldehyde / water = 50 / 50 (mass ratio)). The results are shown in Table 10.

[0163] Example 10-4 1,3-butanediol was produced and evaluated in the same manner as in Example 10-2, except that the raw material liquid was a mixture of acetaldehyde and water (acetaldehyde / water = 50 / 50 (mass ratio)). The results are shown in Table 10.

[0164]

[0165] (Examples 11-1 to 11-4) (1) Preparation of solid base catalyst 11-1 A solid base catalyst was prepared in the same manner as in Example 1-1, except that the magnesia alumina prepared in Example 2-3 was used as the support and the amount of active metal (Mg) supported was changed to 15 mass%, thereby obtaining solid base catalyst 11-1. (2) Production of 1,3-butanediol 1,3-butanediol was produced and evaluated in the same manner as in Examples 10-1 to 10-4, except that the solid base catalyst was changed to solid base catalyst 11-1. The results are shown in Table 11.

[0166]

[0167] Examples 12-1 to 12-4 1,3-butanediol was produced and evaluated in the same manner as in Examples 10-1 to 10-4, except that the solid base catalyst was changed to a calcined product of hydrotalcite calcined at 1100°C (hereinafter referred to as catalyst 12-1). The results are shown in Table 12.

[0168]

[0169] (Examples 13-1 to 13-2) An upflow type flow reactor equipped with two reactors was prepared. The first reactor was packed with the solid base catalyst 3-3 of Example 3-3, and the second reactor was packed with the same hydrogenation catalyst as the hydrogenation catalyst used in Example 1-1. The amounts of each catalyst packed were as shown in Table 13. (2) Production of 1,3-butanediol A mixture of water and acetaldehyde (water / acetaldehyde = 50 / 50 wt / wt) was used as the raw material liquid, and continuous operation was carried out for 168 hours to produce 1,3-butanediol, with the upstream reactor temperature set to 40°C, the downstream reactor temperature set to 70°C, the hydrogen pressure set to 15 MPaG, the hydrogen flow rate set to 5.0 NL / h, and the WHSV set to 0.06 ( / h) in the upstream reactor and 0.08 ( / h) in the downstream reactor. The acetaldehyde conversion (conversion rate (%)) and 1,3-butanediol yield (yield (%)) were determined. The results are shown in Table 13.

[0170]

Claims

1. A method for producing 1,3 - butanediol, comprising a step of bringing a raw material liquid containing acetaldehyde into contact with a solid base catalyst and a hydrogenation catalyst to obtain a reaction liquid containing 1,3 - butanediol, wherein the solid base catalyst contains at least one metal element having an atomic number of 12 to 20, and the hydrogenation catalyst contains Ni.

2. The production method according to claim 1, wherein the step includes a first step of bringing the raw material liquid into contact with the solid base catalyst to obtain a mixed liquid containing acetaldol, and a second step of bringing the mixed liquid into contact with the hydrogenation catalyst to obtain the reaction liquid.

3. The production method according to claim 1, wherein the step is a step of bringing the raw material liquid into contact with a mixture of the solid base catalyst and the hydrogenation catalyst to obtain the reaction liquid.

4. The production method according to claim 1, wherein the step is a step of flowing the raw material liquid through a reactor having a first catalyst layer containing the solid base catalyst and a second catalyst layer containing the hydrogenation catalyst to obtain the reaction liquid.

5. The production method according to any one of claims 1 to 4, wherein the raw material liquid contains at least one polar solvent selected from the group consisting of ethanol and water.

6. The production method according to claim 5, wherein in the raw material liquid, the molar ratio of the polar solvent to acetaldehyde (the polar solvent / acetaldehyde) is 0.3 or more.

7. The production method according to any one of claims 1 to 4, wherein the solid base catalyst includes a carrier and a supported metal supported on the carrier, and the supported metal contains at least one metal element having an atomic number of 12 to 20.

8. The production method according to any one of claims 1 to 4, wherein the solid base catalyst includes an inorganic oxide containing at least one metal element selected from the group consisting of Mg and Al.

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