Catalyst for acetone production and method for producing acetone

Abstract

To provide a catalyst for acetone production and a method for producing acetone which enable acetone to be produced while maintaining a high acetone yield over an extended period.SOLUTION: A catalyst for acetone production includes metal elements of Groups 4, 8, and 12 in the periodic table.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a catalyst for producing acetone and a method for producing acetone.

Background Art

[0002] Conventionally, several reports have been made on the acetone synthesis reaction from ethanol and water. In Non-Patent Document 1, studies have been conducted using a catalyst composed of iron and zinc. In Patent Document 1, studies have been conducted using a catalyst composed of iron and zirconium.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Non-Patent Documents

[0004]

Non-Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] As described above, although several methods for producing acetone from ethanol and water are known, there is room for improvement in producing acetone stably at a high yield for a long time.

[0006] When using a catalyst composed only of iron and zirconium as disclosed in Patent Document 1, since the catalytic activity is low, the acetone yield is low when the reaction is carried out at 500°C or lower, and the catalyst rapidly deteriorates when the reaction is carried out at a temperature exceeding 500°C.

[0007] When using a catalyst composed only of iron and zinc as disclosed in Non-Patent Document 1, the ethanol conversion rate is 90% or more at a reaction temperature of 400 °C, but the acetone selectivity is low, and as a result, the acetone yield is as low as about 50%.

[0008] The present invention has been made in view of these circumstances, and an object thereof is to provide a catalyst for producing acetone and a method for producing acetone that can stably produce acetone with a high acetone yield for a long time in the production of acetone from ethanol and water.

Means for Solving the Problems

[0009] As a result of intensive studies to solve the above problems, the present inventor has arrived at the present invention. That is, the catalyst of the present disclosure is a catalyst for producing acetone containing metal elements of Group 4, Group 8, and Group 12 of the periodic table.

Effects of the Invention

[0010] The present disclosure aims to provide a catalyst for producing acetone and a method for producing acetone that produce acetone with a high yield and stably for a long time.

Modes for Carrying Out the Invention

[0011] Hereinafter, the present disclosure will be described in detail. In addition, a combination of two or more of the individual preferred forms of the present disclosure described below is also a preferred form of the present disclosure. In this specification, "X to Y" indicating a range means "X or more and Y or less".

[0012] [Catalyst for Producing Acetone of the Present Disclosure] <Catalyst> The catalyst of the present disclosure contains a metal element belonging to Group 4 of the periodic table, a metal element belonging to Group 8 of the periodic table, and a metal element belonging to Group 12 of the periodic table.

[0013] The Group 4 metal elements of the periodic table included in the catalyst of this disclosure are preferably titanium, zirconium, and hafnium, and more preferably zirconium. The Group 8 metal elements of the periodic table included in the catalyst of this disclosure are preferably iron, ruthenium, and osmium, and more preferably iron. The Group 12 metal elements of the periodic table included in the catalyst of this disclosure are preferably zinc, cadmium, and mercury, and more preferably zinc. The catalyst of this disclosure more preferably contains iron, zinc, and zirconium.

[0014] The surface composition of metal elements belonging to Group 4 of the periodic table, as measured by X-ray photoelectron spectroscopy (XPS) analysis of the catalyst of this disclosure, is preferably 5 to 50 mol%, more preferably 10 to 40 mol%, and even more preferably 15 to 30 mol%, relative to the total amount of metal elements belonging to Group 4, Group 8, and Group 12 of the periodic table in the entire catalyst of this disclosure.

[0015] The surface composition of metal elements belonging to Group 8 of the periodic table, as measured by X-ray photoelectron spectroscopy (XPS) analysis of the catalyst of this disclosure, is preferably 30 to 90 mol%, more preferably 40 to 80 mol%, and even more preferably 45 to 75 mol%, relative to the total amount of metal elements belonging to Group 4, Group 8, and Group 12 of the periodic table in the entire catalyst of this disclosure.

[0016] The surface composition of metal elements belonging to Group 12 of the periodic table, as measured by X-ray photoelectron spectroscopy (XPS) analysis of the catalyst of this disclosure, is preferably 2 to 60 mol%, more preferably 5 to 40 mol%, and even more preferably 10 to 30 mol%, relative to the total amount of metal elements belonging to Group 4, Group 8, and Group 12 of the periodic table in the entire catalyst of this disclosure.

[0017] The measurement conditions for X-ray photoelectron spectroscopy (XPS) are not particularly limited, but for example, measurements can be taken under the following conditions. Measurement device: Quantera SXM (manufactured by ULVAC-PHI) X-ray output (Al-Kα): 15kV, 20W, beam diameter 100μm X-ray exposure time: 200ms / scan, number of scans: 20

[0018] By setting the surface composition of the catalyst of this disclosure to the above range, coating of the catalyst surface by by-product carbides in the process of reacting ethanol with water is suppressed, and the durability of the catalyst tends to improve.

[0019] The catalysts of this disclosure are not particularly limited and may include other metallic elements. Other metals include, for example, metal elements belonging to Group 1 of the periodic table, such as lithium, sodium, potassium, and cesium (sometimes referred to as alkali metals); metal elements belonging to Group 2 of the periodic table, such as magnesium, calcium, strontium, and barium (sometimes referred to as alkaline earth metals); metal elements belonging to Group 3 of the periodic table, such as scandium, yttrium, and cerium; metal elements belonging to Group 5 of the periodic table, such as vanadium, niobium, and tantalum; metal elements belonging to Group 6 of the periodic table, such as chromium, molybdenum, and tungsten; metal elements belonging to Group 7 of the periodic table, such as manganese, technetium, and rhenium; metal elements belonging to Group 9 of the periodic table, such as cobalt, rhodium, and iridium; metal elements belonging to Group 10 of the periodic table, such as nickel, palladium, and platinum; elements belonging to Group 11 of the periodic table, such as copper, silver, and gold; metal elements belonging to Group 13 of the periodic table, such as aluminum, gallium, indium, and thallium; and metal elements belonging to Group 14 of the periodic table, such as tin and lead.

[0020] The catalyst of this disclosure may contain one or more other metal elements.

[0021] Other metallic elements included in this disclosure are preferably alkali metals, alkaline earth metals, and lanthanide metals, more preferably alkali metals and alkaline earth metals, and even more preferably alkali metals. Preferably alkali metals included in this disclosure are lithium, sodium, potassium, and cesium, and more preferably potassium and cesium.

[0022] The other metal elements contained in the catalyst of this disclosure are preferably 0.01 to 1.0 moles, more preferably 0.02 to 0.2 moles, and even more preferably 0.03 to 0.1 moles, per mole of a metal element from Group 8 of the periodic table. Using these ranges tends to improve the acetone yield.

[0023] The state of the metal element contained in the catalyst of this disclosure is not particularly limited and includes, for example, a metal oxide containing the metal element, a carrier containing the metal element, and a carrier supporting the metal element. The metal oxide may be supported on the carrier. The metal oxide may be a composite metal oxide.

[0024] The catalyst used in this invention may be formed as a catalyst powder on its own, or it may be supported on a carrier such as silica, alumina, silica-alumina, zeolite, silica-calcia, zirconia, titania, ceria, magnesia, steatite, cordierite, silica-magnesia, silica-magnesia-alumina, silicon carbide, silicon nitride, stainless steel, or diatomaceous earth to form a supported material.

[0025] The shape of the catalyst and support used in this invention is not particularly limited, but examples include spherical, pellet-shaped, honeycomb-shaped, ring-shaped, and granular shapes. The dimensions of the catalyst used in this invention are not particularly limited, but the particle size of the catalyst is preferably 1 mm to 12 mm, and more preferably 3 mm to 10 mm. When the catalyst is obtained by molding catalyst powder, the catalyst should be molded to have the above average particle size. When the catalyst is obtained by supporting catalyst powder on a support, a catalyst with the target particle size can be obtained by using a support that is 0.5 to 1.0 mm smaller than the target particle size and adjusting the support time. Here, the particle size of the catalyst refers to its diameter in the case of a spherical catalyst, and to the diameter of the circumscribed sphere of the catalyst in the case of other shapes. When the average particle size of the catalyst is within the above range, it becomes easier to fill the reaction tube with the catalyst and the pressure loss of the catalyst layer can be reduced, thus achieving energy savings such as a reduction in the power consumption of the blower. The average particle size of the catalyst can be measured by measuring the particle size of 100 arbitrarily sampled catalysts with calipers and calculating the average value.

[0026] The catalysts packed into the catalyst layer may be the same shape or different, but it is preferable to pack catalysts of the same shape.

[0027] The state of each element contained in the catalyst of this disclosure is not particularly limited. It may be included as a compound containing a single metal, as an element in a composite metal oxide containing multiple metal elements, or as a support.

[0028] The catalyst of this disclosure preferably contains 0.1 to 1.0 moles of a metal element from Group 12 of the periodic table, more preferably 0.2 to 0.8 moles, and even more preferably 0.25 to 0.75 moles, per mole of iron from Group 8 of the periodic table. A good acetone yield can be obtained by using the above mole range.

[0029] The catalyst of this disclosure preferably contains 0.1 to 1.0 moles of a metal element from Group 4 of the periodic table, more preferably 0.2 to 0.8 moles, and even more preferably 0.25 to 0.75 moles, per mole of a metal element from Group 8 of the periodic table. By using the above mole range, good durability can be achieved.

[0030] The catalyst of this disclosure preferably contains 0.01 to 1.0 moles, more preferably 0.02 to 0.2 moles, and even more preferably 0.03 to 0.1 moles of a metal element from Group 1 of the periodic table, per mole of a metal element from Group 8 of the periodic table. By using the above mole range, a good acetone yield can be obtained.

[0031] The catalyst of this disclosure preferably contains 0.01 to 1.0 moles of a metal element from Group 2 of the periodic table, more preferably 0.02 to 0.2 moles, and even more preferably 0.03 to 0.1 moles, per mole of a metal element from Group 8 of the periodic table. By using the above molar range, a good acetone yield can be obtained.

[0032] <Examples of preferred forms of catalysts for acetone production> The following (1) to (5) are examples of preferred forms of the catalyst for acetone production of the present disclosure. (1) A catalyst for the production of acetone, comprising metal elements from Group 4, Group 8, and Group 12 of the periodic table. (2) The catalyst for acetone production described in (1) above, which contains ZnFe2O4. (3) The catalyst for producing acetone according to (1) or (2) above, wherein the number of moles of a metal element from Group 4 of the periodic table per mole of a metal element from Group 8 of the periodic table is 0.2 to 1.0. (4) The catalyst for producing acetone according to (1) to (3) above, wherein the number of moles of a metal element from Group 12 of the periodic table per mole of a metal element from Group 8 of the periodic table is 0.2 to 1.0. (5) The catalyst for producing acetone according to (1) to (4) above, wherein the number of moles of alkali metals and / or alkaline earth metals per mole of metal elements from Group 8 of the periodic table is 0.02 to 1.0.

[0033] <Method for manufacturing a catalyst> The catalysts of this disclosure are not particularly limited in their manufacturing method and can be produced by, for example, impregnation, precipitation, or coprecipitation. Coprecipitation is more preferred. This method is preferable because it allows for the acquisition of a coprecipitation (sometimes called a catalyst precursor) in which the metal elements that constitute the catalyst are uniformly and highly dispersed, resulting in the production of a catalyst with excellent performance. The composition of each catalyst component in the produced catalyst can be analyzed by X-ray fluorescence analysis (XRF). The coprecipitation method may include steps of adding various catalyst raw materials to water to obtain a precipitate, filtering the coprecipitation, drying the obtained coprecipitation, and calcining. The amount of metal elements in the solution can be changed as appropriate.

[0034] [The method for producing acetone according to this disclosure] The manufacturing method disclosed herein includes a step of reacting ethanol with water in the presence of a catalyst (hereinafter sometimes referred to as the reaction step).

[0035] <Reaction between ethanol and water> The acetone production method of this disclosure can be used to obtain a reaction product containing acetone, hydrogen, and carbon dioxide by contacting ethanol and water, which are raw materials, with a catalyst in the reaction step.

[0036] The acetone production method described herein is not particularly limited and may be either a batch method or a continuous method, but a continuous method is preferred from the viewpoint of productivity.

[0037] The acetone production method of this disclosure is preferably a gas-phase reaction. Examples of gas-phase reaction types include fixed bed, moving bed, and fluidized bed, but the simpler fixed bed type is preferred. If the acetone production method of this disclosure is a fixed-bed type, the raw material gas may be supplied to the reactor after mixing gaseous ethanol and gaseous water (sometimes called water vapor) and then contacting the catalyst, or gaseous ethanol and water vapor may be supplied to the reactor separately and then contacted to the catalyst.

[0038] If the acetone production method of this disclosure is a gas-phase catalytic reaction, it may be a conventional single-flow method or a recycling method.

[0039] Gaseous ethanol can be obtained, for example, by heating liquid ethanol in a vaporizer. Gaseous water can be obtained, for example, by heating water in a vaporizer. The raw material gas may include inert gases such as nitrogen and helium. Here, the raw material gas includes all gases supplied to the reactor.

[0040] The ethanol concentration in the raw material gas is preferably 3 to 66 mol%, and more preferably 5 to 50 mol%. The molar ratio of water to ethanol in the raw material gas is preferably 0.5 to 10, and more preferably 1 to 5. The ethanol used as the raw material gas is not particularly limited. Examples include ethanol obtained by the hydration reaction of ethylene, and bioethanol made from biomass raw materials, such as sugar-based materials like sugarcane, starch-based materials like grains, and cellulose-based materials like plants.

[0041] The ethanol used as the raw material gas preferably contains bioethanol. The bioethanol content in 100% ethanol by mass is preferably 50% by mass or more, more preferably 75% by mass or more, and even more preferably 90% by mass or more.

[0042] The reaction pressure in the acetone production method of this disclosure can be reduced pressure, atmospheric pressure, or pressurized pressure, but is preferably 0.07 MPa to 0.2 MPa, and more preferably 0.1 MPa to 0.15 MPa.

[0043] The reaction temperature in the manufacturing method of this disclosure is preferably 250 to 600°C, more preferably 300 to 500°C, and even more preferably 330 to 450°C.

[0044] In the acetone production method of this disclosure, the space velocity is preferably 100 to 10,000 h⁻¹, more preferably 300 to 8,000 h⁻¹, and even more preferably 500 to 6,000 h⁻¹.

[0045] <Other itineraries> (purification process) The reaction product after contacting ethanol and water with a catalyst may contain not only acetone, hydrogen, and carbon dioxide, but also the raw materials, ethanol and water. The amount of acetone in the reaction product is preferably 2 mol% or more, more preferably 4 mol% or more, and even more preferably 8 mol% or more, based on 100 mol% of the reaction product.

[0046] The acetone production method of this disclosure may include a step of obtaining purified acetone (sometimes called purified acetone) from the reaction product by a known method. Examples include gas-liquid separation and distillation. Gas-liquid separation allows for the separation of the reaction product into a gas such as hydrogen or carbon dioxide and a liquid mixture mainly composed of acetone by a known method. Distillation allows for the obtaining of purified acetone from a liquid mixture containing acetone by a known method. The acetone content in the purified acetone is preferably 90% by mass or more, more preferably 95% by mass or more, and even more preferably 98% by mass or more, based on 100% by mass of purified acetone.

[0047] (Catalyst regeneration process) In the acetone production method of this disclosure, if a change in catalyst activity is observed, a step for regenerating the catalyst may be included. The method of regeneration is not particularly limited, but it can be regenerated by contacting it with an oxidizing gas such as oxygen at a high temperature. For example, if the raw material gas is supplied to a fixed-bed reactor, the raw material gas may be changed to an oxidizing gas, or the catalyst may be removed from the reactor.

[0048] <Examples of preferred forms of methods for producing acetone> The following (6) to (12) are examples of preferred forms of the catalyst for acetone production according to this disclosure. (6) A method for producing acetone, comprising the step of reacting ethanol with water in the presence of a catalyst containing a metal element from Group 4, Group 8, and Group 12 of the periodic table. (7) A method for producing acetone according to (6), comprising the step of reacting ethanol with water in the presence of a catalyst containing ZnFe2O4. (8) A method for producing acetone according to (6) or (7), comprising the step of reacting ethanol with water in the presence of a catalyst in which the number of moles of a metal element from Group 4 of the periodic table per mole of a metal element from Group 8 of the periodic table is 0.2 to 1.0. (9) A method for producing acetone according to (6) to (8), comprising the step of reacting ethanol with water in the presence of a catalyst in which the number of moles of a metal element from Group 12 of the periodic table per mole of a metal element from Group 8 of the periodic table is 0.2 to 1.0. (10) A method for producing acetone according to (6) to (9), comprising the step of reacting ethanol with water in the presence of a catalyst in which the total amount of moles of one or more metal elements selected from the group consisting of alkali metals, alkaline earth metals and lanthanide metals is 0.02 to 1.0 per mole of a metal element from Group 8 of the periodic table. (11) The method for producing acetone according to (6) to (10), wherein the temperature at which ethanol and water are reacted is 300°C to 500°C. (12) The method for producing acetone according to (6) to (11) above, wherein the ethanol is derived from biomass.

[0049] [Acetone production apparatus of this disclosure] The manufacturing apparatus is preferably a fixed-bed reactor. A vaporizer for obtaining the raw material gas may also be connected. The material of the manufacturing apparatus is not particularly limited, but stainless steel is preferred. Representative examples of stainless steel include austenitic stainless steel, such as SUS304, SUS304L, SUS316 and SUS316L of the Japanese Industrial Standards (hereinafter also referred to as JIS); ferritic stainless steel, such as SUS405, SUS401L and SUS430 of JIS; and martensitic stainless steel, such as SUS403, SUS410, SUS416 and SUS431 of JIS.

[0050] [Uses of acetone in this disclosure] The uses of the acetone disclosed herein are not particularly limited, but it can be publicly used as a raw material for the production of isopropyl alcohol. The acetone disclosed herein can be used to produce isopropyl alcohol, for example, by hydrogenation using a known method. [Examples]

[0051] The present invention will be described in more detail below with reference to examples, but the present invention is not limited by the following examples, and it is certainly possible to implement it with appropriate modifications within the scope that is consistent with the spirit of the preceding and following descriptions, and all such modifications are included within the technical scope of the present invention.

[0052] (Example 1) 629 g of zinc nitrate hexahydrate, 562 g of zirconium nitrate dihydrate, 1700 g of iron nitrate nonahydrate, and 1600 g of 28% by weight aqueous ammonia were added to 3800 g of pure water and stirred for 20 hours to obtain a starting material mixture. The obtained starting material mixture was dried in a drum dryer, and the resulting dried material was pulverized and sieved to 150 μm or less to obtain catalyst precursor powder. The obtained catalyst precursor powder was calcined at 450°C for 4 hours in an air atmosphere to obtain catalyst powder. 500 g of the obtained catalyst powder, 5 g of hydroxyethyl cellulose, and 100 g of water were placed in an extruder and molded into a cylindrical shape with a diameter of 6 mm and a length of 6 mm to obtain a pre-calcination catalyst molded body. The obtained pre-calcination catalyst molded body was calcined at 450°C for 4 hours in an air atmosphere to obtain catalyst (1). The metallic element composition of the obtained catalyst (1) is Fe 1.0 Zr 0.5 Zn 0.5 That was the case. Acetone production using catalyst (1) was carried out using a SUS316 U-shaped reactor (outer diameter 25.6 mm, inner diameter 21.6 mm). 140 g of catalyst (1) was packed into a SUS U-shaped reaction tube. The reaction tube packed with catalyst (1) was placed in a molten salt bath, and nitrogen was supplied at 2.6 L / min (at 0°C and 1 atm) to raise the temperature of the molten salt bath to 375°C, where it was maintained for 30 mins. Subsequently, nitrogen, ethanol, and water were supplied at 2.6 L / min (at 0°C and 1 atm), 0.52 L / min (at 0°C and 1 atm), and 2.1 L / min (at 0°C and 1 atm), respectively, and the reaction was carried out. The reaction was carried out continuously for 1000 hours, and the ethanol conversion rate and acetone yield were measured as the reaction time progressed. The results are shown in Table 1. Here, the ethanol conversion rate and acetone yield were calculated using equations (1) and (2). (Formula 1) Ethanol conversion rate = 100 - 100 × Ethanol flow rate at reactor outlet / Ethanol flow rate at reactor inlet (Formula 2) Acetone yield = 100 × acetone flow rate at reactor outlet × 3 / (ethanol flow rate at reactor inlet × 2) The reaction for the synthesis of acetone from ethanol and water is represented by the following reaction equation (3). (Formula 3) 2C2H5OH+H2O→CH3COCH3+CO2+4H2 In equation (2), the acetone yield is evaluated based on the amount of carbon in the produced acetone relative to the total carbon contained in the ethanol supplied to the reactor inlet. Therefore, the maximum acetone yield is 75%. The reactor outlet gas was introduced into an absorption bottle filled with pure water placed in an ice bath, and the components collected by the water were quantified by gas chromatography. Components not collected in the absorption bottle filled with pure water were quantified by introducing the absorption bottle outlet gas into gas chromatography. From these analytical values, the flow rate of each component contained in the reactor outlet gas was calculated, and the ethanol conversion rate and acetone yield were determined using the above equations (1) and (2).

[0053] (Example 2) 629 g of zinc nitrate hexahydrate, 112 g of zirconium oxide nitrate dihydrate, 1700 g of iron nitrate nonahydrate, and 1330 g of 28% by weight aqueous ammonia were added to 3800 g of pure water and stirred for 20 hours to obtain a starting material mixture. The obtained starting material mixture was dried in a drum dryer, and the resulting dried material was pulverized and sieved to 150 μm or less to obtain catalyst precursor powder. The obtained catalyst precursor powder was calcined at 450°C for 4 hours in an air atmosphere to obtain catalyst powder. 500 g of the obtained catalyst powder, 5 g of hydroxyethyl cellulose, and 100 g of water were placed in an extruder and molded into a cylindrical shape with a diameter of 6 mm and a length of 6 mm to obtain a pre-calcination catalyst molded body. The obtained pre-calcination catalyst molded body was calcined at 450°C for 4 hours in an air atmosphere to obtain catalyst (2). The metallic element composition of the obtained reference catalyst (2) is Fe 1.0 Zr 0.1 Zn 0.5 That was the case. Acetone production using catalyst (2) was carried out in the same manner as described in Example 1. The reaction was carried out continuously for 1000 hours, and the ethanol conversion rate and acetone yield were measured as the reaction time progressed. The results are shown in Table 1.

[0054] (Example 3) 629 g of zinc nitrate hexahydrate, 225 g of zirconium nitrate oxide dihydrate, 1700 g of iron nitrate nonahydrate, and 1380 g of 28 wt% aqueous ammonia were added to 3800 g of pure water and stirred for 20 h to obtain a starting material mixture solution. The obtained starting material mixture solution was dried with a drum dryer, and then the obtained dried product was pulverized and sieved to 150 μm or less to obtain a catalyst precursor powder. The obtained catalyst precursor powder was calcined at 450 °C for 4 h in an air atmosphere to obtain a catalyst powder. 500 g of the obtained catalyst powder, 5 g of hydroxyethyl cellulose, and 100 g of water were put into an extrusion molding machine and molded into a cylindrical shape with a diameter of 6 mm × a length of 6 mm to obtain a pre-firing catalyst molded body. The obtained pre-firing catalyst molded body was calcined at 450 °C for 4 h in an air atmosphere to obtain a catalyst (3). The metal element composition of the obtained catalyst (3) was Fe 1.0 Zr 0.2 Zn 0.5 and it was. The production of acetone by catalyst (2) was carried out in the same manner as described in Example 1. The reaction was carried out continuously for 1000 h, and the ethanol conversion rate and acetone yield were measured over time. The results are shown in Table 1.

[0055] (Example 4) 629 g of zinc nitrate hexahydrate, 1124 g of zirconium nitrate oxide dihydrate, 1700 g of iron nitrate nonahydrate, and 1790 g of 28 wt% aqueous ammonia were added to 3800 g of pure water and stirred for 20 h to obtain a starting material mixture solution. The obtained starting material mixture solution was dried with a drum dryer, and then the obtained dried product was pulverized and sieved to 150 μm or less to obtain a catalyst precursor powder. The obtained catalyst precursor powder was calcined at 450 °C for 4 h in an air atmosphere to obtain a catalyst powder. 500 g of the obtained catalyst powder, 5 g of hydroxyethyl cellulose, and 100 g of water were put into an extrusion molding machine and molded into a cylindrical shape with a diameter of 6 mm × a length of 6 mm to obtain a pre-firing catalyst molded body. The obtained pre-firing catalyst molded body was calcined at 450 °C for 4 h in an air atmosphere to obtain a catalyst (4). The metal element composition of the obtained catalyst (4) was Fe 1.0 Zr 1.0 Zn 0.5 and it was. Acetone production using catalyst (4) was carried out in the same manner as described in Example 1. The reaction was carried out continuously for 1000 hours, and the ethanol conversion rate and acetone yield were measured as the reaction time progressed. The results are shown in Table 1.

[0056] (Example 5) 629 g of zinc nitrate hexahydrate, 1349 g of zirconium oxide nitrate dihydrate, 1700 g of iron nitrate nonahydrate, and 1893 g of 28% by weight aqueous ammonia were added to 3800 g of pure water and stirred for 20 hours to obtain a starting material mixture. The obtained starting material mixture was dried in a drum dryer, and the resulting dried material was pulverized and sieved to 150 μm or less to obtain catalyst precursor powder. The obtained catalyst precursor powder was calcined at 450°C for 4 hours in an air atmosphere to obtain catalyst powder. 500 g of the obtained catalyst powder, 5 g of hydroxyethyl cellulose, and 100 g of water were placed in an extruder and molded into a cylindrical shape with a diameter of 6 mm and a length of 6 mm to obtain a pre-calcination catalyst molded body. The obtained pre-calcination catalyst molded body was calcined at 450°C for 4 hours in an air atmosphere to obtain catalyst (5). The metallic element composition of the obtained reference catalyst (5) is Fe 1.0 Zr 1.2 Zn 0.5 That was the case. Acetone production using reference catalyst (5) was carried out in the same manner as described in Example 1. The reaction was carried out continuously for 1000 hours, and the ethanol conversion rate and acetone yield were measured as the reaction time progressed. The results are shown in Table 1.

[0057] (Example 6) 126 g of zinc nitrate hexahydrate, 562 g of zirconium nitrate dihydrate, 1700 g of iron nitrate nonahydrate, and 1125 g of 28% by weight aqueous ammonia were added to 3800 g of pure water and stirred for 20 hours to obtain a starting material mixture. The obtained starting material mixture was dried in a drum dryer, and the resulting dried material was pulverized and sieved to 150 μm or less to obtain catalyst precursor powder. The obtained catalyst precursor powder was calcined at 450°C for 4 hours in an air atmosphere to obtain catalyst powder. 500 g of the obtained catalyst powder, 5 g of hydroxyethyl cellulose, and 100 g of water were placed in an extruder and molded into a cylindrical shape with a diameter of 6 mm and a length of 6 mm to obtain a pre-calcination catalyst molded body. The obtained pre-calcination catalyst molded body was calcined at 450°C for 4 hours in an air atmosphere to obtain catalyst (6). The metallic element composition of the obtained reference catalyst (6) is Fe 1.0 Zr 0.5 Zn 0.1 That was the case. Acetone production using reference catalyst (6) was carried out in the same manner as described in Example 1. The reaction was carried out continuously for 1000 hours, and the ethanol conversion rate and acetone yield were measured as the reaction time progressed. The results are shown in Table 1.

[0058] (Example 7) 251 g of zinc nitrate hexahydrate, 562 g of zirconium nitrate dihydrate, 1700 g of iron nitrate nonahydrate, and 1228 g of 28% by weight aqueous ammonia were added to 3800 g of pure water and stirred for 20 hours to obtain a starting material mixture. The obtained starting material mixture was dried in a drum dryer, and the resulting dried material was pulverized and sieved to 150 μm or less to obtain catalyst precursor powder. The obtained catalyst precursor powder was calcined at 450°C for 4 hours in an air atmosphere to obtain catalyst powder. 500 g of the obtained catalyst powder, 5 g of hydroxyethyl cellulose, and 100 g of water were placed in an extruder and molded into a cylindrical shape with a diameter of 6 mm and a length of 6 mm to obtain a pre-calcination catalyst molded body. The obtained pre-calcination catalyst molded body was calcined at 450°C for 4 hours in an air atmosphere to obtain catalyst (7). The metallic element composition of the obtained catalyst (7) is Fe 1.0 Zr 0.5 Zn 0.2 That was the case. Acetone production using catalyst (7) was carried out in the same manner as described in Example 1. The reaction was carried out continuously for 1000 hours, and the ethanol conversion rate and acetone yield were measured as the reaction time progressed. The results are shown in Table 1.

[0059] (Example 8) 1257 g of zinc nitrate hexahydrate, 562 g of zirconium nitrate dihydrate, 1700 g of iron nitrate nonahydrate, and 2046 g of 28% by weight aqueous ammonia were added to 3800 g of pure water and stirred for 20 hours to obtain a starting material mixture. The obtained starting material mixture was dried in a drum dryer, and the resulting dried material was pulverized and sieved to 150 μm or less to obtain catalyst precursor powder. The obtained catalyst precursor powder was calcined at 450°C for 4 hours in an air atmosphere to obtain catalyst powder. 500 g of the obtained catalyst powder, 5 g of hydroxyethyl cellulose, and 100 g of water were placed in an extruder and molded into a cylindrical shape with a diameter of 6 mm and a length of 6 mm to obtain a pre-calcination catalyst molded body. The obtained pre-calcination catalyst molded body was calcined at 450°C for 4 hours in an air atmosphere to obtain catalyst (8). The metallic element composition of the obtained catalyst (8) is Fe 1.0 Zr 0.5 Zn 1.0 That was the case. Acetone production using catalyst (8) was carried out in the same manner as described in Example 1. The reaction was carried out continuously for 1000 hours, and the ethanol conversion rate and acetone yield were measured as the reaction time progressed. The results are shown in Table 1.

[0060] (Example 9) 1508 g of zinc nitrate hexahydrate, 562 g of zirconium oxide nitrate dihydrate, 1700 g of iron nitrate nonahydrate, and 2251 g of 28% by weight aqueous ammonia were added to 3800 g of pure water and stirred for 20 hours to obtain a starting material mixture. The obtained starting material mixture was dried in a drum dryer, and the resulting dried material was pulverized and sieved to 150 μm or less to obtain a catalyst precursor powder. The obtained catalyst precursor powder was calcined at 450°C for 4 hours in an air atmosphere to obtain catalyst powder. 500 g of the obtained catalyst powder, 5 g of hydroxyethyl cellulose, and 100 g of water were placed in an extruder and molded into a cylindrical shape with a diameter of 6 mm and a length of 6 mm to obtain a pre-calcination catalyst molded body. The obtained pre-calcination catalyst molded body was calcined at 450°C for 4 hours in an air atmosphere to obtain catalyst (9). The metallic element composition of the obtained reference catalyst (9) is Fe 1.0 Zr 0.5 Zn 1.2 That was the case. Acetone production using reference catalyst (9) was carried out in the same manner as described in Example 1. The reaction was carried out continuously for 1000 hours, and the ethanol conversion rate and acetone yield were measured as the reaction time progressed. The results are shown in Table 1.

[0061] (Example 10) 629 g of zinc nitrate hexahydrate, 562 g of zirconium oxide nitrate dihydrate, 1700 g of iron nitrate nonahydrate, 8.2 g of cesium nitrate, and 1537 g of 28% by weight aqueous ammonia were added to 3800 g of pure water and stirred for 20 hours to obtain a starting material mixture. The obtained starting material mixture was dried in a drum dryer, and the resulting dried material was pulverized and sieved to 150 μm or less to obtain catalyst precursor powder. The obtained catalyst precursor powder was calcined at 450°C for 4 hours in an air atmosphere to obtain catalyst powder. 500 g of the obtained catalyst powder, 5 g of hydroxyethyl cellulose, and 100 g of water were placed in an extruder and molded into a cylindrical shape with a diameter of 6 mm and a length of 6 mm to obtain a pre-calcination catalyst molded body. The obtained pre-calcination catalyst molded body was calcined at 450°C for 4 hours in an air atmosphere to obtain catalyst (10). The metallic element composition of the obtained catalyst (10) is Fe 1.0 Zr 0.5 Zn 0.5 Cs 0.01 That was the case. Acetone production using catalyst (10) was carried out in the same manner as described in Example 1. The reaction was carried out continuously for 1000 hours, and the ethanol conversion rate and acetone yield were measured as the reaction time progressed. The results are shown in Table 1.

[0062] (Example 11) 629 g of zinc nitrate hexahydrate, 562 g of zirconium oxide nitrate dihydrate, 1700 g of iron nitrate nonahydrate, 16.4 g of cesium nitrate, and 1540 g of 28% by weight aqueous ammonia were added to 3800 g of pure water and stirred for 20 hours to obtain a starting material mixture. The obtained starting material mixture was dried in a drum dryer, and the resulting dried material was pulverized and sieved to 150 μm or less to obtain a catalyst precursor powder. The obtained catalyst precursor powder was calcined at 450°C for 4 hours in an air atmosphere to obtain catalyst powder. 500 g of the obtained catalyst powder, 5 g of hydroxyethyl cellulose, and 100 g of water were placed in an extruder and molded into a cylindrical shape with a diameter of 6 mm and a length of 6 mm to obtain a pre-calcination catalyst molded body. The obtained pre-calcination catalyst molded body was calcined at 450°C for 4 hours in an air atmosphere to obtain catalyst (11). The metallic element composition of the obtained catalyst (11) is Fe 1.0 Zr 0.5 Zn 0.5 Cs 0.02 That was the case. Acetone production using catalyst (11) was carried out in the same manner as described in Example 1. The reaction was carried out continuously for 1000 hours, and the ethanol conversion rate and acetone yield were measured as the reaction time progressed. The results are shown in Table 1.

[0063] (Example 12) 629 g of zinc nitrate hexahydrate, 562 g of zirconium oxide nitrate dihydrate, 1700 g of iron nitrate nonahydrate, 32.8 g of cesium nitrate, and 1545 g of 28% by weight aqueous ammonia were added to 3800 g of pure water and stirred for 20 hours to obtain a starting material mixture. The obtained starting material mixture was dried in a drum dryer, and the resulting dried material was pulverized and sieved to 150 μm or less to obtain catalyst precursor powder. The obtained catalyst precursor powder was calcined at 450°C for 4 hours in an air atmosphere to obtain catalyst powder. 500 g of the obtained catalyst powder, 5 g of hydroxyethyl cellulose, and 100 g of water were placed in an extruder and molded into a cylindrical shape with a diameter of 6 mm and a length of 6 mm to obtain a pre-calcination catalyst molded body. The obtained pre-calcination catalyst molded body was calcined at 450°C for 4 hours in an air atmosphere to obtain catalyst (12). The metallic element composition of the obtained catalyst (12) is Fe 1.0 Zr 0.5 Zn 0.5 Cs 0.04 That was the case. Acetone production using catalyst (12) was carried out in the same manner as described in Example 1. The reaction was carried out continuously for 1000 hours, and the ethanol conversion rate and acetone yield were measured as the reaction time progressed. The results are shown in Table 1.

[0064] (Example 13) 629 g of zinc nitrate hexahydrate, 562 g of zirconium oxide nitrate dihydrate, 1700 g of iron nitrate nonahydrate, 164 g of cesium nitrate, and 1586 g of 28% by weight aqueous ammonia were added to 3800 g of pure water and stirred for 20 hours to obtain a starting material mixture. The obtained starting material mixture was dried in a drum dryer, and the resulting dried material was pulverized and sieved to 150 μm or less to obtain catalyst precursor powder. The obtained catalyst precursor powder was calcined at 450°C for 4 hours in an air atmosphere to obtain catalyst powder. 500 g of the obtained catalyst powder, 5 g of hydroxyethyl cellulose, and 100 g of water were placed in an extruder and molded into a cylindrical shape with a diameter of 6 mm and a length of 6 mm to obtain a pre-calcination catalyst molded body. The obtained pre-calcination catalyst molded body was calcined at 450°C for 4 hours in an air atmosphere to obtain catalyst (13). The metallic element composition of the obtained catalyst (13) is Fe 1.0 Zr 0.5 Zn 0.5 Cs 0.2 That was the case. Acetone production using catalyst (13) was carried out in the same manner as described in Example 1. The reaction was carried out continuously for 1000 hours, and the ethanol conversion rate and acetone yield were measured as the reaction time progressed. The results are shown in Table 1.

[0065] (Example 14) 629 g of zinc nitrate hexahydrate, 562 g of zirconium oxide nitrate dihydrate, 1700 g of iron nitrate nonahydrate, 4.3 g of potassium nitrate, and 1537 g of 28% by weight aqueous ammonia were added to 3800 g of pure water and stirred for 20 hours to obtain a starting material mixture. The obtained starting material mixture was dried in a drum dryer, and the resulting dried material was pulverized and sieved to 150 μm or less to obtain catalyst precursor powder. The obtained catalyst precursor powder was calcined at 450°C for 4 hours in an air atmosphere to obtain catalyst powder. 500 g of the obtained catalyst powder, 5 g of hydroxyethyl cellulose, and 100 g of water were placed in an extruder and molded into a cylindrical shape with a diameter of 6 mm and a length of 6 mm to obtain a pre-calcination catalyst molded body. The obtained pre-calcination catalyst molded body was calcined at 450°C for 4 hours in an air atmosphere to obtain catalyst (14). The metallic element composition of the obtained catalyst (14) is Fe 1.0 Zr 0.5 Zn 0.5 K 0.01 That was the case. Acetone production using catalyst (14) was carried out in the same manner as described in Example 1. The reaction was carried out continuously for 1000 hours, and the ethanol conversion rate and acetone yield were measured as the reaction time progressed. The results are shown in Table 1.

[0066] (Example 15) 629 g of zinc nitrate hexahydrate, 562 g of zirconium oxide nitrate dihydrate, 1700 g of iron nitrate nonahydrate, 213 g of potassium nitrate, and 1663 g of 28% by weight aqueous ammonia were added to 3800 g of pure water and stirred for 20 hours to obtain a starting material mixture. The obtained starting material mixture was dried in a drum dryer, and the resulting dried material was pulverized and sieved to 150 μm or less to obtain catalyst precursor powder. The obtained catalyst precursor powder was calcined at 450°C for 4 hours in an air atmosphere to obtain catalyst powder. 500 g of the obtained catalyst powder, 5 g of hydroxyethyl cellulose, and 100 g of water were placed in an extruder and molded into a cylindrical shape with a diameter of 6 mm and a length of 6 mm to obtain a pre-calcination catalyst molded body. The obtained pre-calcination catalyst molded body was calcined at 450°C for 4 hours in an air atmosphere to obtain catalyst (15). The metallic element composition of the obtained catalyst (15) is Fe 1.0 Zr 0.5 Zn 0.5 K 0.5 That was the case. Acetone production using catalyst (15) was carried out in the same manner as described in Example 1. The reaction was carried out continuously for 1000 hours, and the ethanol conversion rate and acetone yield were measured as the reaction time progressed. The results are shown in Table 1.

[0067] (Example 16) 629 g of zinc nitrate hexahydrate, 562 g of zirconium oxide nitrate dihydrate, 1700 g of iron nitrate nonahydrate, 425 g of potassium nitrate, and 1790 g of 28% by weight aqueous ammonia were added to 3800 g of pure water and stirred for 20 hours to obtain a starting material mixture. The obtained starting material mixture was dried in a drum dryer, and the resulting dried material was pulverized and sieved to 150 μm or less to obtain a catalyst precursor powder. The obtained catalyst precursor powder was calcined at 450°C for 4 hours in an air atmosphere to obtain catalyst powder. 500 g of the obtained catalyst powder, 5 g of hydroxyethyl cellulose, and 100 g of water were placed in an extruder and molded into a cylindrical shape with a diameter of 6 mm and a length of 6 mm to obtain a pre-calcination catalyst molded body. The obtained pre-calcination catalyst molded body was calcined at 450°C for 4 hours in an air atmosphere to obtain reference catalyst (16). The metallic element composition of the obtained catalyst (16) is Fe 1.0 Zr 0.5 Zn 0.5 K 1.0 That was the case. Acetone production using reference catalyst (16) was carried out in the same manner as described in Example 1. The reaction was carried out continuously for 1000 hours, and the ethanol conversion rate and acetone yield were measured as the reaction time progressed. The results are shown in Table 1.

[0068] (Comparative Example 1) 553 g of zinc nitrate hexahydrate, 727 g of aluminum nitrate notahydrate, 1700 g of iron nitrate notahydrate, and 1280 g of 28% by weight aqueous ammonia were added to 2660 g of pure water and stirred for 20 hours to obtain a starting material mixture. The obtained starting material mixture was dried in a drum dryer, and the resulting dried material was pulverized and sieved to 150 μm or less to obtain catalyst precursor powder. The obtained catalyst precursor powder was calcined at 450°C for 4 hours in an air atmosphere to obtain catalyst powder. 500 g of the obtained catalyst powder, 5 g of hydroxyethyl cellulose, and 100 g of water were placed in an extruder and molded into a cylindrical shape with a diameter of 6 mm and a length of 6 mm to obtain a pre-calcination catalyst molded body. The obtained pre-calcination catalyst molded body was calcined at 450°C for 4 hours in an air atmosphere to obtain catalyst (17). The metallic element composition of the obtained catalyst (17) is Fe 1.0 Al 0.1 Zn 0.4 That was the case. Acetone production using catalyst (17) was carried out in the same manner as described in Example 1. The reaction was carried out continuously for 1000 hours, and the ethanol conversion rate and acetone yield were measured as the reaction time progressed. The results are shown in Table 1.

[0069] [Table 1]

[0070] As can be seen from Table 1, the degradation of the catalyst over time is suppressed, and the reaction can be carried out for a long time while maintaining a high acetone yield.

Claims

1. comprising zirconium, iron and zinc, The molar ratio of zirconium to 1 mole of iron is 0.2 to 1.

0. A catalyst for acetone production, wherein the molar ratio of zinc to 1 mole of iron is 0.2 to 1.

0.

2. The catalyst for producing acetone according to Claim 1, wherein the catalyst further comprises one or more other metal elements selected from the group consisting of alkali metals, alkaline earth metals, and lanthanide metals, and the ratio of the total amount of moles of the other metal elements to one mole of iron is 0.02 to 1.

0.

3. comprising zirconium, iron and zinc, The molar ratio of zirconium to 1 mole of iron is 0.2 to 1.

0. A method for producing acetone, comprising the step of reacting ethanol with water in the presence of a catalyst in which the molar ratio of zinc to 1 mole of iron is 0.2 to 1.

0.

4. The method for producing acetone according to claim 3, wherein the catalyst further comprises one or more other metal elements selected from the group consisting of alkali metals, alkaline earth metals, and lanthanide metals, and the ratio of the total amount of moles of the other metal elements to one mole of iron is 0.02 to 1.

0.

5. A method for producing acetone according to claim 3 or 4, wherein the temperature at which ethanol and water are reacted is 300°C to 500°C.

6. A method for producing acetone according to claim 3 or 4, wherein the ethanol is derived from biomass.

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