Method for producing catalyst

Abstract

Provided is a method for producing a catalyst for producing 1,3-butadiene from a feedstock containing ethanol. The method includes: a heat treatment step in which an element (A) is immobilized on a support by heat treating a mixture comprising the support, water, and a water solubility modifier with which the water solubility of the element (A) selected from the group consisting of Group 4 and Group 5 elements of the periodic table has been modified, such heat treatment being performed under conditions in which the heat treatment temperature is 100°C or or higher but is no greater than the boiling point of water; and a drying / calcinating step in which the mixture is dried and calcinated after the heat treatment step. The support does not include zeolite.

Description

Catalyst manufacturing method

[0001] The present invention relates to a method for producing a catalyst for producing 1,3-butadiene from a raw material containing ethanol. This application claims priority to PCT / JP2024 / 014683 filed on April 11, 2024, the contents of which are incorporated herein by reference.

[0002] The ETB (Ethanol to Butadiene) process for producing 1,3-butadiene from raw materials containing ethanol includes a single-stage process (Lebedev process) in which ethanol is converted to butadiene in one stage, and a two-stage process (Ostromislensky process) in which ethanol is first dehydrogenated to synthesize acetaldehyde, and then butadiene is synthesized from ethanol and acetaldehyde. Known ETB catalysts used in the ETB process include catalysts in which elements of Groups 4 and 5 of the periodic table are supported on silica (Patent Documents 1 and 2). Patent Document 3 discloses a butadiene production catalyst containing zeolite.

[0003] Japanese Patent No. 6803289 Japanese Patent No. 7227209 Japanese Special Publication No. 2016-521719

[0004] The present invention provides a novel method for producing a catalyst that can provide high 1,3-butadiene selectivity and high 1,3-butadiene yield.

[0005] As a result of intensive research aimed at solving the above-mentioned problems, the present inventors have completed the present invention with the following configuration. [1] A method for producing a catalyst for producing 1,3-butadiene from a raw material containing ethanol, the method comprising: a heat treatment step of heat-treating a mixture containing a water-soluble preparation of an element (A) selected from Groups 4 and 5 of the periodic table, a support, and water, at a heat treatment temperature of 100°C or higher under conditions that are equal to or lower than the boiling point of water, thereby immobilizing the element (A) on the support; and a drying and calcination step of drying and calcining the mixture after the heat treatment step, wherein the support does not contain zeolite. [2] A method for producing a catalyst according to [1], wherein the heat treatment step is performed in the presence of liquid water. [3] A method for producing a catalyst according to [1] or [2], wherein the heat treatment step is performed at a temperature in the range of 120°C to 200°C. [4] A method for producing a catalyst according to [1] or [2], wherein the heat treatment step is performed at a temperature in the range of 140°C to 180°C. [5] The method for producing a catalyst according to any one of [1] to [4], wherein the heat treatment step is carried out under acidic conditions. [6] The method for producing a catalyst according to any one of [1] to [5], wherein the element (A) is at least one selected from zirconium, hafnium, and tantalum. [7] The method for producing a catalyst according to any one of [1] to [6], wherein the element (A) is tantalum, and the water-soluble preparation is tantalum oxalate. [8] The method for producing a catalyst according to any one of [1] to [7], wherein the drying and calcining step includes a drying step of drying the mixture after the heat treatment step, and a calcining step of calcining the mixture after the drying step at 110°C to 600°C. [9] The method for producing a catalyst according to any one of [1] to [8], further including a mixture production step of immersing the support in an aqueous solution of the water-soluble preparation to produce the mixture prior to the heat treatment step.

[10] The method for producing a catalyst according to [9], wherein the support has pores, and the aqueous solution of the water-soluble preparation is in an amount that is 0.3 times or more the volume of the pores and 10 times or less the volume of the support.

[11] The method for producing a catalyst according to any one of [1] to

[10] , further comprising, prior to the heat treatment step, a mixture production step of adding water to a dried product containing the water-soluble preparation and the support to produce the mixture.

[12] The method for producing a catalyst according to

[11] , wherein in the mixture production step, the dried product is produced by immersing the support in an aqueous solution of the water-soluble preparation and then drying it.

[13] The method for producing a catalyst according to

[11] or

[12] , wherein the support has pores, and the volume of water added to the dried product is 0.3 times or more the volume of the pores and 10 times or less the volume of the support.

[0006] According to the present invention, it is possible to provide a novel method for producing a catalyst that can provide high 1,3-butadiene selectivity and high 1,3-butadiene yield.

[0007] 1 is a graph showing the 1,3-butadiene selectivity of the catalysts prepared in Examples 1 to 6 and Comparative Example 1.

[0008] Hereinafter, embodiments for carrying out the present invention will be described.

[0009] The catalyst produced in this embodiment is a catalyst for producing 1,3-butadiene from a raw material containing ethanol, and includes an element (A) selected from the group consisting of Groups 4 and 5 of the Periodic Table, and a support.

[0010] Examples of the element (A) include titanium, zirconium, hafnium, vanadium, niobium, tantalum, etc. From the viewpoint of improving the 1,3-butadiene selectivity and the 1,3-butadiene yield, it is preferable that the element (A) is at least one selected from zirconium, hafnium, and tantalum.

[0011] Examples of the carrier include silicon dioxide, mesoporous silica, and zeolite. When using zeolite, the carrier can be synthesized by adding element (A) at the stage of the zeolite precursor, but when the carrier does not contain zeolite, the carrier itself used for the catalyst can be subjected to the heat treatment step. When zeolite is not used, the carrier may be silicon dioxide alone. Examples of silicon dioxide include amorphous silica, silica sol, silica gel, and colloidal silica. Examples of mesoporous silica include MCM-41, FSM-16, and SBA-15.

[0012] The manufacturing method of this embodiment includes a heat treatment step in which a mixture containing a water-soluble preparation adjusted to the water solubility of element (A), a carrier, and water is heat-treated, and a drying / calcination step in which the mixture after the heat treatment step is dried and calcined. In the heat treatment step, element (A) is immobilized on the carrier. In immobilizing element (A) on the carrier, it is preferable that element (A) is supported on the carrier, and further, it is preferable that element (A) and the carrier are chemically bonded. In the following description, the water-soluble preparation of element (A) may be simply referred to as the water-soluble preparation.

[0013] Examples of the water-soluble preparation include compounds or compositions prepared so that the element (A) is water-soluble. For example, the element (A) may be an organic acid salt such as oxalic acid, glycolic acid, lactic acid, malic acid, or citric acid, or an inorganic compound such as a chloride. Examples of organic acids include carboxylic acids such as monocarboxylic acids, dicarboxylic acids, and hydroxycarboxylic acids. When the element (A) is tantalum, the water-soluble preparation may be tantalum oxalate. When the element (A) is hafnium, the water-soluble preparation may be hafnium chloride. When the element (A) is zirconium, the water-soluble preparation may be zirconyl chloride. The use of a water-soluble preparation of the element (A) makes the element (A) more easily dispersible in a mixture containing the water-soluble preparation and water (such as an aqueous solution of the water-soluble preparation), and facilitates interaction with the carrier during the heat treatment process.

[0014] (Heat Treatment Step) In the heat treatment step, heat treatment is performed at a heat treatment temperature of 100°C or higher, and the heat treatment temperature is equal to or lower than the boiling point of water. The heat treatment temperature is preferably in the range of 100°C to 200°C, and may be in the range of 120°C to 200°C, or even in the range of 140°C to 180°C. By performing the heat treatment step, the element (A) may be chemically bonded to the carrier. In this case, for example, a step of desorbing an organic substance such as oxalic acid contained in the water-soluble preparation from the element (A) may be included.

[0015] As shown in Figure 1, the selectivity of 1,3-butadiene can be improved by carrying out the heat treatment step in the range of 120°C to 200°C. In addition, the selectivity of 1,3-butadiene can be further improved by carrying out the heat treatment step in the range of 140°C to 180°C. On the other hand, even when the temperature is relatively low, the selectivity of 1,3-butadiene can be improved by extending the heat treatment time.

[0016] When element (A) is released from the water-soluble preparation, the water solubility at room temperature and normal pressure may decrease, but the above-mentioned heat treatment conditions can maintain or increase the solubility of element (A). The element (A) forms a chemical bond with the support, thereby obtaining a catalyst whose activity is stably maintained. The heat treatment step may be a process in which a substance in which element (A) and the support are chemically bonded is synthesized according to a hydrothermal treatment method.

[0017] The heat treatment step may be performed under conditions in which liquid water is present. The high-temperature conditions under which liquid water is present may be higher than atmospheric pressure (approximately 0.1 MPa). When the heat treatment step is performed under high-pressure conditions, an autoclave may be used.

[0018] The heat treatment pressure (treatment pressure in the heat treatment step) can be, for example, 0.1 to 1.6 MPa, or even 0.2 to 1.1 MPa. The vapor pressure in the container during treatment at 140 to 180°C can be 0.37 to 1.02 MPa, and the vapor pressure during treatment at a temperature of 120 to 200°C can be 0.2 to 1.6 MPa. The heat treatment pressure may be equal to or greater than the saturated vapor pressure of water at the heat treatment temperature. The heat treatment time (treatment time in the heat treatment step) varies depending on the amount of the mixture, the performance of the treatment device, etc., and is not particularly limited, but can be, for example, 5 min to 100 h.

[0019] The heat treatment step is preferably carried out under acidic conditions. If necessary, a pH adjuster may be added to the mixture. The pH of the mixture containing the water-soluble preparation and water (at room temperature: approximately 25°C) to achieve the acidic conditions is preferably 0.5 to 6.0, more preferably 0.8 to 4.0, even more preferably 1.0 to 3.0, and particularly preferably 1.2 to 2.0. By carrying out the heat treatment step under acidic conditions, the burden on the support can be reduced. If the heat treatment step is carried out at a pH of 7.0 or higher, the element (A) will precipitate in the mixture containing the water-soluble preparation and water (such as an aqueous solution of the water-soluble preparation), resulting in a decrease in catalytic performance. Furthermore, the support is likely to become brittle. Therefore, the heat treatment step is preferably carried out under acidic conditions.

[0020] (Mixture Production Step 1) The production method of this embodiment may include a mixture production step of immersing a carrier in an aqueous solution of a water-soluble preparation to produce a mixture containing the water-soluble preparation, the carrier, and water prior to the heat treatment step. In this case, the production method of this embodiment includes the mixture production step, the heat treatment step, and the drying / calcination step.

[0021] In the mixture production step, if the carrier has pores, the volume of the aqueous solution of the water-soluble preparation may be 0.3 times or more (or 0.9 times or more) the volume of the pores and 10 times or less the volume of the carrier. The volume of the carrier may be the total volume of the carrier to be immersed. At least a portion or all of the pores may be filled with the aqueous solution. The aqueous solution of the water-soluble preparation may be absorbed into the pores of the carrier, or the aqueous solution of the water-soluble preparation may be present in a liquid phase outside the carrier. The ratio of the volume of the aqueous solution to the volume of the pores may be in the range of 0.3 to 15, 0.6 to 10, or 0.9 to 3.0. Regardless of whether the carrier has pores or not, the ratio of the volume of the aqueous solution to the volume of the carrier may be in the range of 0.2 to 10, 0.5 to 5.0, or 0.8 to 2.0.

[0022] (Mixture Production Step 2) The production method of this embodiment may include a mixture production step in which, prior to the heat treatment step, water is added to a dried product containing the water-soluble preparation and the carrier to produce a mixture containing the water-soluble preparation, the carrier, and water. In this mixture production step, the dried product may be produced by immersing the carrier in an aqueous solution of the water-soluble preparation and then drying. In this case, the production method of this embodiment includes a dried product production step, a mixture production step, a heat treatment step, and a drying / calcination step.

[0023] When a dried product production step is performed, the element (A) may be supported on a carrier during drying. In this case, in the dried product, the element (A) may be supported on a carrier in the form of a water-soluble preparation, or the element (A) may not be chemically bonded to the carrier.

[0024] In the step of adding water to the dried product, at least a portion of the water-soluble preparation contained in the dried product may be dissolved or wet. While the carrier is wet, at least a portion of the water-soluble preparation may remain in a dry state. When the carrier has pores, the volume of water added to the dried product may be 0.3 times or more (or 0.9 times or more) the volume of the pores and 10 times or less the volume of the carrier. In the step of immersing the carrier in the aqueous solution of the water-soluble preparation, at least a portion or all of the pores may be filled with the aqueous solution. The aqueous solution of the water-soluble preparation may be absorbed into the pores of the carrier, or the aqueous solution of the water-soluble preparation may exist in a liquid phase outside the carrier. In the dried product, water may volatilize, and the solid of the water-soluble preparation may remain on the outer surface or in the pores of the carrier. The ratio of the volume of water added to the dried product to the volume of the pores may be in the range of 0.3 to 15, 0.6 to 10, or 0.9 to 3.0. Regardless of whether the carrier has pores or not, the ratio of the volume of water added to the dried product to the volume of the carrier may be in the range of 0.2 to 10, 0.5 to 5.0, or 0.8 to 2.0.

[0025] (Drying and Firing Step) The drying and firing step may include a drying step of drying the mixture after the heat treatment step, and a firing step of firing the mixture after the drying step at 110°C to 600°C. The firing temperature (treatment temperature in the firing step) may be 110°C to 550°C, 150°C to 500°C, or 200°C to 450°C. The drying temperature (treatment temperature in the drying step) may be 70°C to 150°C, or 90°C to 120°C. The drying temperature may be lower than the firing temperature. Drying and firing of the mixture may proceed in one step.

[0026] The catalyst of this embodiment is produced by calcining the mixture. That is, after the calcination step, the catalyst production process is completed without performing additional steps such as modification with Si. Therefore, the catalyst after the calcination step is ready for use as a product. Even if the number of steps is reduced by omitting the Si modification, high 1,3-butadiene selectivity and high 1,3-butadiene yield can be obtained.

[0027] The drying time (treatment time for the drying step) is not particularly limited, but may be 5 minutes to 100 hours. The firing time (treatment time for the firing step) is not particularly limited, but may be 5 minutes to 100 hours. The drying / firing time (treatment time for the drying / firing step) is not particularly limited, but may be 5 minutes to 200 hours, or even 10 minutes to 100 hours. These treatment times vary depending on the amount of the mixture, the performance of the treatment device, etc., and can be set appropriately.

[0028] The drying and firing process may be carried out at a temperature at which the water contained in the mixture after the heat treatment process can be evaporated and at a temperature equal to or higher than the decomposition temperature of the water-soluble preparation. For example, the firing process may be carried out in the range of 110°C to 600°C, 110°C to 400°C, or 150°C to 250°C. In this embodiment, for example, when tantalum oxalate is used as the water-soluble preparation, the firing process may be carried out at a temperature equal to or higher than the decomposition temperature of tantalum oxalate. Alternatively, when tantalum oxalate is decomposed into tantalum oxide and oxalic acid after the heat treatment process, the firing process may be carried out at a temperature equal to or higher than the decomposition temperature of oxalic acid.

[0029] When Si modification is omitted, the catalyst of this embodiment can be produced, for example, without including a reaction product with a silicon compound having a hydrolyzable group. Here, a silicon compound having a hydrolyzable group is a compound in which 1 to 4 hydrolyzable groups are bonded to a silicon atom. Examples of the hydrolyzable group include hydrogen, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, and an alkenyloxy group. A silicon compound having a hydrolyzable group is represented, for example, by the following formula (1): SiY ｎ R （４－ｎ） ...(1)

[0030] In formula (1), each Y is independently a hydrolyzable group. R is a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. n is an integer of 1 to 4. The substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms is not particularly limited, and examples include alkyl groups having 1 to 20 carbon atoms (methyl, ethyl, propyl, etc.), aryl groups having 6 to 20 carbon atoms (phenyl, tolyl, etc.), and aralkyl groups having 7 to 20 carbon atoms (benzyl, phenethyl, etc.). When two or more Y or R are bonded, they may be the same or different. Furthermore, the silicon compound having a hydrolyzable group may be a partial polycondensate in which at least a portion has been polycondensed.

[0031] In the catalyst production method of this embodiment, when the Si modification is omitted, the mixture containing the water-soluble preparation, the carrier, and water prior to the heat treatment step may be a mixture that does not contain the silicon compound having a hydrolyzable group. 29 When the signal intensity of the maximum value in the Si-NMR chemical shift value near −111 ppm is taken as 1, the signal intensity at the chemical shift value −105 ppm may be less than 0.55.

[0032] The catalyst of this embodiment may contain, in addition to the element (A) and the carrier, metals such as zinc, silver, copper, and gold, alkali metals, alkaline earth metals, lanthanoids, etc. The shape of the catalyst is not particularly limited, and known shapes such as granular, columnar, cylindrical, and honeycomb shapes can be used.

[0033] [Method for Producing 1,3-Butadiene] The method for producing 1,3-butadiene using the catalyst of this embodiment is characterized by bringing a raw material containing at least ethanol into contact with the catalyst under heating. The origin of the ethanol is not particularly limited, and examples thereof include ethanol derived from biomass such as sugarcane or corn, or from petroleum, coal, or natural gas. The use of biomass-derived ethanol can contribute to reducing greenhouse gas emissions.

[0034] The raw material may be ethanol alone, or may contain acetaldehyde together with ethanol. When acetaldehyde is contained, the molar ratio of ethanol to acetaldehyde (EtOH:AcH) is in the range of 95:5 to 40:60, preferably 90:10 to 50:50, and more preferably 85:15 to 50:50.

[0035] The reaction conditions are not particularly limited, and well-known systems such as a batch system, a semi-batch system, a continuous system, etc. A continuous system allows for large-scale synthesis, reduces the operational workload, and reuses unreacted raw materials in the reaction system to improve the utilization rate of raw material ethanol, thereby enabling simple and efficient separation and recovery of 1,3-butadiene.

[0036] Examples of methods for contacting the raw material with the catalyst include a suspension bed method, a fluidized bed method, and a fixed bed method. The raw material may be supplied by either a gas phase method or a liquid phase method, with the gas phase method being preferred. When the reaction is carried out in the gas phase, the raw material gas may be supplied to the reactor without dilution, or may be supplied to the reactor after being appropriately diluted with an inert gas such as nitrogen, helium, argon, or water vapor. During the reaction, acetaldehyde may be added to the raw material containing ethanol to adjust the molar ratio (EtOH:AcH) to the above-mentioned ratio.

[0037] After completion of the reaction, the reaction product can be separated and purified into light gases, C4 fractions, heavy components, water, ethanol, acetaldehyde, etc., by separation means such as distillation or extraction, or a combination thereof. The above-mentioned catalyst can be used for the efficient production of 1,3-butadiene, and therefore has high industrial applicability.

[0038] The present invention will be explained in more detail below with reference to examples, but the present invention is not limited to these examples in any way.

[0039] (Example 1) As a water-soluble preparation of the element (A), an aqueous solution of tantalum oxalate (TANiOBIS, Ta ２ O ５ 192 g / L) was used. The pH of the tantalum oxalate aqueous solution was approximately 1.5. 0.82 g of the tantalum oxalate aqueous solution was further diluted by adding 14.10 g of distilled water. The pH of the diluted tantalum oxalate aqueous solution was approximately 2.0. Spherical silica having a particle size of 1.18 to 2.36 mm was used as the carrier. 10.00 g of spherical silica was added to the diluted tantalum oxalate aqueous solution to obtain a mixture containing a water-soluble preparation of element (A), a carrier, and water. The moisture content of a sample of the mixture containing the water-soluble preparation, a carrier, and water was measured using a moisture meter manufactured by KETT Corporation and was found to be 50 to 60%.

[0040] A mixture containing a water-soluble preparation, a carrier, and water: about 4.00 cm ３ The mixture was placed in a container in a wet state, placed in an autoclave, and subjected to hydrothermal treatment at 160°C for 10 hours. The container had an outer cylinder made of SUS and an inner cylinder made of polytetrafluoroethylene (PTFE), and had a capacity of approximately 50 cm ３ The following items were used.

[0041] Comparative Example 1 Hydrothermal treatment was carried out in the same manner as in Example 1, except that the hydrothermal treatment temperature was changed to 80°C.

[0042] Example 2 Hydrothermal treatment was carried out in the same manner as in Example 1, except that the hydrothermal treatment temperature was changed to 100°C.

[0043] Example 3 Hydrothermal treatment was carried out in the same manner as in Example 1, except that the hydrothermal treatment temperature was changed to 120°C.

[0044] Example 4 Hydrothermal treatment was carried out in the same manner as in Example 1, except that the hydrothermal treatment temperature was changed to 140°C.

[0045] Example 5 Hydrothermal treatment was carried out in the same manner as in Example 1, except that the hydrothermal treatment temperature was changed to 180°C.

[0046] Example 6 Hydrothermal treatment was carried out in the same manner as in Example 1, except that the hydrothermal treatment temperature was changed to 200°C.

[0047] Example 7 The hydrothermal treatment was carried out in the same manner as in Example 3, except that the hydrothermal treatment time was set to 36 hours.

[0048] (Example 8) As a water-soluble preparation of the element (A), an aqueous solution of tantalum oxalate (TANiOBIS, Ta ２ O ５ 192 g / L) was used. The pH of the tantalum oxalate aqueous solution was approximately 1.5. 1.14 g of the tantalum oxalate aqueous solution was further diluted by adding 30.57 g of distilled water. The pH of the diluted tantalum oxalate aqueous solution was approximately 1.8. Spherical silica having a particle size of 1.18 to 2.36 mm was used as the carrier. 10.00 g of spherical silica was added to the diluted tantalum oxalate aqueous solution to obtain a mixture containing a water-soluble preparation of element (A), the carrier, and excess water.

[0049] The entire mixture containing the water-soluble preparation, the carrier, and excess water was placed in a container, which was then placed in an autoclave and subjected to hydrothermal treatment at 160°C for 10 hours. The container had an outer cylinder made of SUS and an inner cylinder made of polytetrafluoroethylene (PTFE), and had a capacity of approximately 50 cm3. ３ The following items were used.

[0050] Comparative Example 2 As a water-soluble preparation of the element (A), an aqueous solution of tantalum oxalate (TANiOBIS, Ta ２ O ５A tantalum oxalate aqueous solution (178 g / L) was used. The pH of the tantalum oxalate aqueous solution was approximately 1.5. 1.16 g of the tantalum oxalate aqueous solution was further diluted by adding 30.56 g of distilled water. The pH of the diluted tantalum oxalate aqueous solution was approximately 1.8. Spherical silica with a particle size of 1.18 to 2.36 mm was used as the carrier. 10.00 g of spherical silica was added to the diluted tantalum oxalate aqueous solution to obtain a mixture containing a water-soluble preparation of element (A), the carrier, and excess water. A tetraethylammonium hydroxide aqueous solution (Sigma-Aldrich, 35 wt%) was then added to adjust the pH to 10.

[0051] The entire mixture containing the water-soluble preparation, the carrier, and excess water, and further adjusted to pH 10 with a tetraethylammonium hydroxide aqueous solution, was placed in a container, charged into an autoclave, and subjected to hydrothermal treatment at 160 ° C. for 10 hours. The container had an outer cylinder made of SUS and an inner cylinder made of polytetrafluoroethylene (PTFE), and had a capacity of approximately 50 cm ３ The following items were used.

[0052] (Example 9) As a water-soluble preparation of the element (A), an aqueous solution of tantalum oxalate (TANiOBIS, Ta ２ O ５ 178 g / L) was used. The pH of the tantalum oxalate aqueous solution was approximately 1.5. 3.74 g of the tantalum oxalate aqueous solution was further diluted by adding 41.23 g of distilled water. The pH of the diluted tantalum oxalate aqueous solution was approximately 1.8. Spherical silica with a particle size of 1.18 to 2.36 mm was used as the carrier. 30.00 g of spherical silica was added to the diluted tantalum oxalate aqueous solution to obtain a mixture containing a water-soluble preparation of element (A), the carrier, and water. This was dried at 60°C for 10 hours to obtain a dried product containing the water-soluble preparation and the carrier.

[0053] 6 g of the dried product containing the water-soluble preparation and the carrier and 18.92 g of distilled water were placed in a container, charged into an autoclave, and subjected to hydrothermal treatment at 160 ° C. for 10 hours. The container had an outer cylinder made of SUS and an inner cylinder made of polytetrafluoroethylene (PTFE), and had a capacity of approximately 50 cm ３ The following items were used.

[0054] Example 10 Hydrothermal treatment was carried out in the same manner as in Example 1, except that the amount of the tantalum oxalate aqueous solution was changed to 0.83 g and the amount of distilled water was changed to 12.61 g.

[0055] Example 11 Hydrothermal treatment was carried out in the same manner as in Example 1, except that the amount of the tantalum oxalate aqueous solution was changed to 0.83 g and the amount of distilled water was changed to 9.66 g.

[0056] Example 12 Hydrothermal treatment was carried out in the same manner as in Example 1, except that the amount of the tantalum oxalate aqueous solution was changed to 0.83 g and the amount of distilled water was changed to 6.70 g.

[0057] Example 13 Hydrothermal treatment was carried out in the same manner as in Example 1, except that the amount of the tantalum oxalate aqueous solution was changed to 0.83 g and the amount of distilled water was changed to 3.74 g.

[0058] (Example 14) Hydrothermal treatment was carried out in the same manner as in Example 1, except that 0.182 g of hafnium chloride was used as the water-soluble preparation of element (A), the amount of distilled water was changed to 26.21 g, and the amount of spherical silica was changed to 20.00 g.

[0059] Comparative Example 3 In the same manner as in Example 14, a mixture containing a water-soluble preparation, a carrier, and water was produced at room temperature (about 25°C), and used as a raw material for producing a catalyst without carrying out hydrothermal treatment.

[0060] (Example 15) Hydrothermal treatment was carried out in the same manner as in Example 1, except that 0.357 g of zirconyl chloride was used as the water-soluble preparation of element (A), the amount of distilled water was changed to 26.31 g, and the amount of spherical silica was changed to 20.00 g.

[0061] Comparative Example 4 In the same manner as in Example 15, a mixture containing a water-soluble preparation, a carrier, and water was produced at room temperature (about 25°C), and used as a raw material for producing a catalyst without carrying out hydrothermal treatment.

[0062] (Catalyst Production) In Examples 1 to 13 and Comparative Examples 1 and 2, the mixture after the hydrothermal treatment was dried at 120°C for 10 hours and then calcined at 200°C for 6 hours. In Examples 14 and 15, the mixture after the hydrothermal treatment was dried at 120°C for 10 hours and then calcined at 450°C for 6 hours. In Comparative Examples 3 and 4, the mixture produced without hydrothermal treatment was dried at 90°C for 10 hours and then calcined at 450°C for 6 hours.

[0063] (Production of 1,3-butadiene using the catalyst) Using the obtained catalyst, a process for producing 1,3-butadiene (BD) from a raw material containing ethanol was carried out. 0.95 g of the catalyst, crushed to 300 to 710 μm, was packed into an SUS reaction tube with an inner diameter of 8 mm. A mixed raw material of ethanol and acetaldehyde adjusted to a molar ratio of 80:20 was added at a WHSV of 1.0 h. －１ The reaction was carried out at a reaction temperature of 330° C. and a raw material partial pressure of 0.26 MPaA.

[0064] The composition of the mixture and other information are shown in Table 1. The catalyst production conditions, as well as the results of measuring the raw material conversion, BD selectivity, and BD yield during BD production, are shown in Table 2. The pore volume was calculated as the amount of water absorption (volume) obtained by drying the support at 120°C for 2 hours, allowing the support to cool to room temperature (approximately 25°C) in a desiccator, and then immersing the support in pure water from the weight difference before and after immersion. The support volume was calculated from the weight and packing density of the support.

[0065] As shown in Table 2, in Examples 1 to 15, high BD selectivity and BD yield were obtained by using a water-soluble preparation in which the element (A) was adjusted to be water-soluble, and by performing heat treatment under conditions where the heat treatment temperature was 100°C or higher and below the boiling point of water. In Comparative Example 1, the hydrothermal treatment temperature was low, resulting in decreased BD selectivity and BD yield. In Comparative Example 2, the pH during heat treatment was high, making the support brittle and decreasing the raw material conversion rate. In Comparative Examples 3 and 4, the BD selectivity and BD yield decreased when hydrothermal treatment was not performed.

[0066]

[0067]

[0068] In Table 2, the value corresponding to the ratio of the amount of aqueous solution (the amount of water added to the dried product in Example 9) to the volume of the pores is shown as "aqueous solution or water / pore volume," and the value corresponding to the ratio of the amount of aqueous solution (the amount of water added to the dried product in Example 9) to the volume of the carrier is shown as "aqueous solution or water / carrier volume."

[0069] The catalyst of the present invention can be used for producing 1,3-butadiene from a raw material containing ethanol.

Claims

1. A method for producing a catalyst for producing 1,3-butadiene from a raw material containing ethanol, A heat treatment step comprising: a heat treatment step in which a mixture containing a water-soluble preparation of an element (A) selected from the group consisting of groups 4 and 5 of the periodic table, a support, and water is heat-treated at a heat treatment temperature of 100°C or higher, under conditions that the heat treatment temperature is below the boiling point of water, thereby immobilizing the element (A) on the support; A drying and firing step in which the mixture after the heat treatment step is dried and fired, A method for producing a catalyst, wherein the carrier does not contain zeolite.

2. The method for producing a catalyst according to claim 1, wherein the heat treatment step is performed under conditions in which liquid water is present.

3. The method for producing a catalyst according to claim 1 or 2, wherein the heat treatment step is carried out in the range of 120°C to 200°C.

4. The method for producing a catalyst according to claim 1 or 2, wherein the heat treatment step is carried out in the range of 140°C to 180°C.

5. The method for producing a catalyst according to claim 1 or 2, wherein the heat treatment step is carried out under acidic conditions.

6. The method for producing a catalyst according to claim 1 or 2, wherein the element (A) is at least one selected from zirconium, hafnium, and tantalum.

7. The method for producing a catalyst according to claim 1 or 2, wherein the element (A) is tantalum and the water-soluble modifier is tantalum oxalate.

8. The method for producing a catalyst according to claim 1 or 2, wherein the drying and calcination step comprises a drying step of drying the mixture after the heat treatment step and a calcination step of calcining the mixture after the drying step at 110°C to 600°C.

9. A method for producing a catalyst according to claim 1 or 2, comprising a mixture production step prior to the heat treatment step, in which the carrier is immersed in an aqueous solution of the water-soluble modifier to produce the mixture.

10. The method for producing a catalyst according to claim 9, wherein the carrier has pores, and the aqueous solution of the water-soluble modifier is in an amount of 0.3 times or more the volume of the pores and 10 times or less the volume of the carrier.

11. A method for producing a catalyst according to claim 1 or 2, comprising a mixture production step prior to the heat treatment step, in which water is added to a dried product containing the water-soluble modifier and the carrier to produce the mixture.

12. The method for producing a catalyst according to claim 11, wherein in the mixture production step, the dried product is produced by immersing the carrier in an aqueous solution of the water-soluble adjuster and then drying it.

13. The method for producing a catalyst according to claim 11, wherein the carrier has pores, and the volume of water added to the dried product is 0.3 times or more the volume of the pores and 10 times or less the volume of the carrier.