Acetone hydrogenation catalyst and method for producing isopropanol

Abstract

To provide a catalyst for use in an acetone hydrogenation reaction which has high activity and can produce isopropanol even in low-temperature conditions such as without external heating.SOLUTION: An acetone hydrogenation catalyst includes a metal element of Group 10 in the periodic table and a metal oxide with an acid strength (H0 constant) of +7.2 or more.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a Group 10 metal element-supported catalyst useful for the production of isopropanol by acetone catalytic hydrogenation, and to a method for producing isopropanol by acetone catalytic hydrogenation using the catalyst. [Background technology]

[0002] The reaction to obtain isopropanol by hydrogenating acetone in the presence of hydrogen using a catalyst has been known for a long time (Patent Document 1). Catalysts disclosed include nickel-based catalysts (Patent Document 1), copper-based catalysts (Patent Document 2), ruthenium-based catalysts (Patent Document 3), and platinum-based catalysts (Patent Document 4).

[0003] Many reaction methods for the acetone hydrogenation reaction have been disclosed, including batch reactions in the liquid phase and trickle bed reactions (Patent Document 5).

[0004] On the other hand, regarding the gas phase, there have been few proposals for isopropanol production methods using catalysts effective for the acetone hydrogenation reaction (Patent Document 6). [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Unexamined Patent Publication No. 62-012729 [Patent Document 2] Japanese Patent Publication No. 2010-077055 [Patent Document 3] Japanese Patent Publication No. 2000-103751 [Patent Document 4] Japanese Patent Publication No. 2009-207976 [Patent Document 5] Japanese Unexamined Patent Publication No. 2-270829 [Patent Document 6] Japanese Patent Publication No. 2002-128716 [Overview of the project] [Problems that the invention aims to solve]

[0006] In acetone hydrogenation reactions, for example, in liquid-phase acetone hydrogenation reactions including trickle bed reactions, the elution of catalyst components is prone to occur, making it difficult to suppress the decrease in catalytic activity. In gas-phase reactions, there is still room for improvement in catalysts that can efficiently produce isopropanol by acetone hydrogenation.

[0007] Therefore, the present invention aims to provide a catalyst that has high activity in the hydrogenation reaction of acetone and can produce isopropanol even in low temperature ranges, for example, without external heating. [Means for solving the problem]

[0008] The inventors of the present invention have arrived at this invention as a result of diligent research to solve the above problems. Specifically, the catalyst of this disclosure is an acetone hydrogenation catalyst comprising a metal element of Group 10 of the periodic table and a metal oxide having an acid strength (H0 constant) of +7.2 or higher. [Effects of the Invention]

[0009] According to the present invention, it is possible to provide an acetone hydrogenation catalyst that can produce isopropanol by hydrogenating acetone even in low-temperature ranges, such as near room temperature without external heating. [Modes for carrying out the invention]

[0010] The present disclosure is described in detail below. Furthermore, any combination of two or more of the individual preferred forms of the present disclosure described below also constitutes a preferred form of the present disclosure.

[0011] [Acetone Hydrogenation Catalyst] <Group 10 elements of the periodic table> The acetone hydrogenation catalyst of the present disclosure (hereinafter also referred to as the catalyst of the present disclosure) contains at least one metal element belonging to Group 10 of the periodic table. Examples of the metal element belonging to Group 10 of the periodic table include Ni, Pd, and Pt. The catalyst of the present disclosure may contain only one kind of metal element belonging to Group 10 of the periodic table, or may contain two or more kinds.

[0012] The form of the metal element belonging to Group 10 of the periodic table contained in the catalyst of the present disclosure is not particularly limited. For example, it may be contained as a metal or as an oxide.

[0013] The proportion of the metal element of Group 10 of the periodic table contained in the catalyst of the present disclosure is preferably 0.1 to 20% by mass, more preferably 0.2 to 10% by mass, and still more preferably 0.3 to 5% by mass, based on the total amount of the catalyst of the present disclosure.

[0014] The catalyst of the present disclosure more preferably contains Pt.

[0015] The catalyst of the present disclosure may contain other metal elements. For example, metal elements belonging to Group 1 of the periodic table such as Li, Na, K, Rb, Cs; metal elements belonging to Group 2 of the periodic table such as Be, Mg, Ca, Sr, Ba; metal elements belonging to Group 3 of the periodic table such as Sc, Y, La, Ce; metal elements belonging to Group 4 of the periodic table such as Ti, Zr, Hf; metal elements belonging to Group 5 of the periodic table such as V, Nb, Ta; metal elements belonging to Group 6 of the periodic table such as Cr, Mo, W; metal elements belonging to Group 7 of the periodic table such as Mn, Tc, Re; metal elements belonging to Group 8 of the periodic table such as Fe, Ru, Os; metal elements belonging to Group 9 of the periodic table such as Co, Rh, Ir; elements belonging to Group 11 of the periodic table such as Cu, Ag, Au; Group 12 elements such as Zn, Cd, Hg; metal elements belonging to Group 13 of the periodic table such as Al, Ga, In, Tl, metal elements belonging to Group 14 of the periodic table such as Sn, Pb, etc. can be mentioned.

[0016] The catalyst of the present disclosure may contain only one kind of other metal element, or may contain two or more kinds. The form of the other metal element contained in the catalyst of the present disclosure is not particularly limited. For example, it may be contained as a metal or as an oxide.

[0017] The proportion of other metal elements contained in the catalyst of the present disclosure is preferably 0.1 to 20% by mass, more preferably 0.2 to 15% by mass, and still more preferably 0.3 to 10% by mass, based on the total amount of the catalyst of the present disclosure.

[0018] As the other metal elements contained in the catalyst of the present disclosure, preferably, those belonging to Group 1, Group 2, Group 3, and Group VIII of the periodic table are mentioned.

[0019] In the catalyst of the present disclosure, the metal element may be contained as a metal oxide or a carrier described below.

[0020] <Metal oxide> The catalyst of the present disclosure contains a metal oxide. The catalyst of the present disclosure may contain only one kind of metal oxide or two or more kinds of metal oxides.

[0021] The catalyst of the present disclosure contains one or more metal oxides having an acid strength (H0) (hereinafter, sometimes simply referred to as "acid strength" or "H0") of +7.2 or more.

[0022] The metal oxide contained in the catalyst of the present disclosure is more preferably such that the acid strength of the metal oxide is preferably +7.2 or more, more preferably +8.0 or more. On the other hand, it is preferably +22.3 or less, more preferably +17.2 or less.

[0023] The shape of the metal oxide of the present disclosure is not particularly limited, and examples include powdery, particulate, pellet shape, honeycomb shape, etc. The crystal structure of the metal oxide of the present disclosure is not particularly limited, and examples include tetragonal, hexagonal, trigonal, orthorhombic, monoclinic, triclinic, wurtzite-type crystal, etc. The metal oxide of the present disclosure may be a single metal oxide or a composite metal oxide.

[0024] The metal oxide contained in the catalyst of the present disclosure is preferably an oxide of a metal element belonging to Groups 2 to 15 of the periodic table, more preferably an oxide of a metal element belonging to Groups 2 to 4 of the periodic table.

[0025] Examples of metal oxides included in the catalyst of this disclosure include magnesium oxide (MgO), calcium oxide (CaO), strontium oxide (SrO), yttrium oxide (Y2O3), cerium oxide (CeO2), lanthanum oxide (La2O3), zirconium oxide (ZrO2), zinc oxide (ZnO), and CeO2-ZrO2. More preferably, CeO2, ZrO2, and MgO are used, and even more preferably, CeO2 and ZrO2.

[0026] The proportion of metal oxides contained in the catalyst of this disclosure is preferably 50 to 99.9% by mass, more preferably 60 to 99% by mass, and even more preferably 70 to 95% by mass, based on the total amount of the catalyst of this disclosure.

[0027] The metal oxide contained in the catalyst of this disclosure is preferably a carrier that supports the metal element. The specific surface area of ​​the carrier is 1 to 500 m². 2 It is preferable that the amount be / g, and more preferably 2 to 400m 2 / g, and more preferably 5-300m 2 It is / g.

[0028] <Examples of preferred forms of acetone hydrogenation catalysts> The following (1) to (4) are examples of preferred forms of the acetone hydrogenation catalyst of this disclosure. (1) An acetone hydrogenation catalyst comprising a metal element from Group 10 of the periodic table and a metal oxide having an acid strength (H0 constant) of +7.2 or higher. (2) The acetone hydrogenation catalyst according to (1), wherein the content of metal elements from Group 10 of the periodic table is 0.1 to 10% by mass. (3) The acetone hydrogenation catalyst according to (1) or (2), wherein the metal oxide is zirconium oxide and / or cerium oxide. (4) The acetone hydrogenation catalyst described in (1) to (3) above, wherein the metal element of Group 10 of the periodic table is platinum.

[0029] [Method for producing an acetone hydrogenation catalyst] The method for producing the acetone hydrogenation catalyst of this disclosure is not particularly limited and may be produced by known methods. For example, it can be produced by solid-phase reaction, impregnation, precipitation, coprecipitation, etc. For example, it may be produced by mixing solid raw materials such as oxides or carbonates of constituent elements and calcining, by adding an aqueous solution containing a salt of another constituent element to an oxide of one constituent element, mixing and impregnating, drying and calcining, or by mixing an aqueous solution containing a salt of a constituent element, adjusting the pH to obtain a precipitate, and then drying and calcining the precipitate. Examples of the constituent elements include metal elements belonging to Group 10 of the periodic table, other metal elements, and metal elements that constitute metal oxides. It may also be produced by mixing a solution or slurry of a compound containing a metal element belonging to Group 10 of the periodic table with a metal oxide as needed, drying and then calcining.

[0030] Examples of compounds containing metal elements belonging to Group 10 of the periodic table include, but are not limited to, platinum compounds such as chloroplatinic acid, sodium chloroplatinate, potassium chloroplatinate, ammonium chloroplatinate, hexahydrooxoplatinic acid, dinitrodiammineplatinic acid, hexaammineplatinate chloride, hexaammineplatinate hydroxylate, hexaammineplatinate nitrate, tetraammineplatinate chloride, tetraammineplatinate hydroxylate, tetraammineplatinate nitrate, ammonium ethanol hexahydroxoplatinate, and platinum acetylacetonate; nickel compounds such as nickel nitrate hexahydrate, nickel acetate tetrahydrate, and nickel sulfate hexahydrate; and palladium compounds such as palladium chloride, tetraamminepalladium chloride, tetraamminepalladium hydroxylate, and dinitrodiamminepalladium nitrate. These may be used individually or in combination of two or more.

[0031] The solvents used in solutions and slurries of compounds containing metal elements belonging to Group 10 of the periodic table are not particularly limited, but examples include water; alcohols such as ethanol, isopropanol, ethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, glycerin, and pentaerythritol; and so on. These may be used individually or in combination of two or more.

[0032] The metal oxide is not particularly limited, but examples include the compounds exemplified in the "acetone hydrogenation catalyst" described above.

[0033] The mixing may be carried out with stirring. The mixing may be carried out at room temperature, but it may also be carried out under cooling or heating conditions. The mixing process may also be carried out under an inert gas atmosphere such as nitrogen or argon.

[0034] The method for producing the catalyst of this disclosure may include a molding step. The molding step is not particularly limited, but for example, one or more metal oxides may be thoroughly mixed in a mixer such as a kneader in the presence of molding aids such as an organic binder or glass fiber as needed, the solid content may be adjusted as needed, and the mixture may be extruded into a predetermined shape. After drying and firing the molded product, the catalyst of this disclosure may be produced by supporting a metal element belonging to Group 10 of the periodic table on it by impregnation or the like.

[0035] The firing temperature is not particularly limited, but is preferably 200 to 600°C, more preferably 250 to 550°C, and even more preferably 300 to 500°C. The firing may be carried out at a constant temperature, or it may be carried out under two or more temperature conditions. The firing process may be carried out under an inert gas atmosphere such as nitrogen or argon. The firing time is not particularly limited, but is preferably 10 minutes or more and 10 hours or less, and more preferably 30 minutes or more and 5 hours or less.

[0036] [Method for producing isopropanol] In the manufacturing method disclosed herein, an isopropanol-containing gas is obtained by reacting acetone with hydrogen in the presence of a catalyst.

[0037] <Raw material supply process> The method for producing isopropanol according to this disclosure includes a step of supplying raw materials containing hydrogen and acetone to a catalyst layer containing a catalyst that includes at least one metal element belonging to Group 10 of the periodic table and a metal oxide having an acid strength (H0 constant) of +7.2 or higher (hereinafter also referred to as the raw material supply step). There are no particular restrictions on the form in which the raw materials are supplied to the catalyst layer, but the raw material components may be supplied to the reactor containing the catalyst layer as a gas, or one or more of the raw material components may be supplied to the reactor containing the catalyst layer as a liquid and vaporized in the reactor to supply the raw materials to the catalyst layer. A gasification device such as a heating furnace may be provided in front of the reactor containing the catalyst layer.

[0038] In this disclosure, the term "catalyst layer" should be understood in the usual sense, for example, as the part of a reactor that is filled with or contains a catalyst. The raw materials may include hydrogen and acetone, but are not particularly limited, and the hydrogen and acetone may be prepared separately.

[0039] The catalyst used in the raw material supply process, which includes at least one metal element belonging to Group 10 of the periodic table and a metal oxide with an acid strength (H0 constant) of +7.2 or higher, is the same as the catalyst used in the acetone hydrogenation process described later, which includes at least one metal element belonging to Group 10 of the periodic table and a metal oxide with an acid strength (H0 constant) of +7.2 or higher.

[0040] The raw materials, hydrogen and acetone, may be added to the reactor as a mixture, or they may be added to the reactor separately.

[0041] The shape of the reactor is not particularly limited. For example, it may be a fixed-bed flow reactor. The material of the reactor is also not particularly limited. For example, it may be a reactor made of stainless steel (SUS).

[0042] The concentration of acetone in the raw material is preferably 2% by volume or more and 50% by volume or less, more preferably 5% by volume or more and 45% by volume or less, and even more preferably 10% by volume or more and 40% by volume or less. The above is usually the concentration supplied to the catalyst layer (i.e., the concentration at which acetone etc. is vaporized).

[0043] The ratio of hydrogen concentration to acetone concentration in the raw material is preferably 1.1 to 5, and more preferably 1.2 to 3. If the ratio of hydrogen concentration to acetone concentration in the raw material is less than 1.1, the acetone conversion rate tends to decrease. If the ratio of hydrogen concentration to acetone concentration in the raw material exceeds 5, side reactions such as the hydrocracking reaction of acetone and isopropanol tend to proceed more easily.

[0044] The raw materials are optional and may include inert gases such as nitrogen or helium. The raw materials are optional and may include water, methane, carbon monoxide, etc. However, since carbon monoxide tends to adsorb to the active metal of the acetone hydrogenation catalyst and reduce the acetone hydrogenation activity, it is preferable that the concentration of carbon monoxide in the raw materials be less than 20 ppm by volume.

[0045] The temperature of the raw material gas supplied to the catalyst layer can be adjusted as appropriate by heating the supplied raw material with a heater. Preferably, the temperature is 20 to 100°C, more preferably 20 to 90°C, and even more preferably 20 to 80°C.

[0046] <Acetone Hydrogenation Process> The method for producing isopropanol according to this disclosure includes a step of hydrogenating acetone (hereinafter also referred to as the acetone hydrogenation step). The acetone hydrogenation step is carried out in the presence of a catalyst comprising at least one metal element belonging to Group 10 of the periodic table and a metal oxide having an acid strength (H0 constant) of +7.2 or higher. The catalyst described in this disclosure above is a preferred example of a catalyst comprising at least one metal element belonging to Group 10 of the periodic table and a metal oxide having an acid strength (H0 constant) of +7.2 or higher. The catalyst comprising at least one metal element belonging to Group 10 of the periodic table and a metal oxide having an acid strength (H0 constant) of +7.2 or higher may be used in one or more types. When two or more catalysts comprising at least one metal element belonging to Group 10 of the periodic table and a metal oxide having an acid strength (H0 constant) of +7.2 or higher are used, they may be mixed, packed in a tandem structure, or packed separately into two or more reactors.

[0047] The method for producing isopropanol according to this disclosure may also use, in addition to a catalyst comprising at least one metal element belonging to Group 10 of the periodic table and a metal oxide having an acid strength (H0 constant) of +7.2 or higher, for example, a known acetone hydrogenation catalyst.

[0048] The acetone hydrogenation process is preferably carried out by a gas-phase reaction. The reaction format by the gas-phase reaction is not particularly limited and can include fixed bed, moving bed, and fluidized bed, but the simpler fixed bed format is preferred.

[0049] In the acetone hydrogenation step, the reaction pressure is preferably 0.1 MPa to 2 MPa, and more preferably 0.1 MPa to 1.0 MPa.

[0050] The reaction temperature in the acetone hydrogenation step is preferably 20°C to 100°C, and more preferably 20°C to 80°C. Lower reaction temperatures are advantageous in equilibrium, but hydrogenation tends to be less likely to proceed. On the other hand, higher reaction temperatures tend to result in a lower acetone hydrogenation conversion rate due to equilibrium constraints, and in addition, hydrocracking of acetone and isopropanol occurs concurrently, leading to a decrease in yield.

[0051] Here, the reaction temperature in the acetone hydrogenation process is the temperature of the raw material gas supplied to the catalyst layer in the acetone hydrogenation process. The temperature of the raw material gas supplied to the catalyst layer can be adjusted as appropriate. The method of adjusting the temperature is not particularly limited, but specific examples include electric heaters and heat exchangers. For example, when using an electric heater, the temperature of the electric heater is preferably 20 to 100°C, more preferably 20 to 90°C, and even more preferably 20 to 80°C.

[0052] The space velocity in the acetone hydrogenation process is preferably 200 to 200,000 (1 / h), more preferably 1,000 to 100,000 (1 / h), and even more preferably 4,000 to 20,000 (1 / h).

[0053] The acetone hydrogenation step includes a step of hydrogenating acetone in a reactor containing a catalyst layer to which raw materials are supplied, as described in the raw material supply step. If two or more reactors are used in the acetone hydrogenation step, at least one of them should be a reactor containing a catalyst layer to which raw materials are supplied, as described in the raw material supply step.

[0054] <Other processes> The method for producing isopropanol according to this disclosure may include any steps other than the raw material supply step and the acetone hydrogenation step (hereinafter also referred to as "other steps").

[0055] (Acetone manufacturing process) The method for producing isopropanol according to this disclosure may include a step of reacting ethanol with water in the presence of a catalyst to obtain acetone (hereinafter also referred to as the acetone production step). Preferably, part or all of the ethanol is bioethanol.

[0056] The catalyst used in the acetone production process is not particularly limited, but it should contain various metal elements, preferably alkali metals, alkaline earth metals, iron, manganese, zinc, copper, aluminum, zirconium, and other elements. Among these, it is preferable to contain iron from the viewpoint of catalytic activity. More preferably, it is preferable to contain iron (Fe) and one or more metals (Me) selected from the group consisting of magnesium (Mg), calcium (Ca), manganese (Mn), and zinc (Zn).

[0057] The state of the metal element contained in the catalyst used in the acetone production process is not particularly limited, and examples include 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 a carrier. The metal oxide may be a composite metal oxide. Examples of composite metal oxides include spinel type, perovskite type, magnetoprumbite type, and garnet type, but spinel type is preferred.

[0058] Examples of catalysts used in the aforementioned acetone production process include iron composite oxides (sometimes called ferrites), represented by the general formula MeO·nFe2O3 (where Me represents one or more metals selected from the group consisting of Mg, Ca, Mn, and Zn, and n represents an integer from 1 to 6).

[0059] The catalyst used in the acetone production process preferably contains 0.4 to 0.7 moles, more preferably 0.4 to 0.6 moles, and even more preferably 0.45 to 0.55 moles, of one or more metals (Me) selected from the group consisting of magnesium, calcium, manganese, and zinc, per mole of iron. Within this range, catalytic activity tends to improve.

[0060] The catalyst used in the acetone production process preferably contains 0.01 to 1 mole of zirconium per mole of iron, more preferably 0.1 to 0.8 moles, and even more preferably 0.2 to 0.6 moles. Using this range tends to improve durability.

[0061] The catalyst used in the acetone production process preferably contains one or more metals (Me) selected from the group consisting of magnesium, calcium, manganese, and zinc, iron, and zirconium in a total amount of 50 to 100% by mass, and more preferably 80 to 100% by mass, relative to 100% by mass of the catalyst.

[0062] In the aforementioned acetone production process, a reaction product containing acetone, hydrogen, and carbon dioxide can be obtained by contacting the raw materials, ethanol and water, with a catalyst. The reaction equation is as follows:

[0063] 2C2H5OH+H2O → CH3COCH3+4H2+CO2 The acetone production process may be carried out in a batch manner, but from the viewpoint of productivity, it is preferable to carry it out in a continuous manner. The acetone production process may be carried out as a liquid-phase reaction, but it is preferable to carry it out as a gas-phase reaction. Examples of gas-phase reaction forms include fixed bed, moving bed, and fluidized bed, but the simpler fixed bed form is preferred. In the case of a fixed bed form, the raw materials may be a mixture of gaseous ethanol and gaseous water (sometimes called water vapor) which is then supplied to the reactor and brought into contact with the catalyst, or gaseous ethanol and water vapor may be supplied to the reactor separately and brought into contact with the catalyst. The raw materials (hereinafter sometimes referred to as raw material gas) may contain inert gases such as nitrogen and helium. Here, raw material gas includes all gases supplied to the reactor.

[0064] In the acetone production process described above, 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.

[0065] In the acetone production process described above, 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. In the acetone production process described above, it is preferable that the ethanol used as the raw material gas contains bioethanol. The bioethanol content in 100% by mass of ethanol is more preferably 50% by mass or more, even more preferably 75% by mass or more, and even more preferably 90% by mass or more.

[0066] In the acetone production process described above, the reaction pressure can be reduced, atmospheric, or pressurized, but is preferably 0.07 MPa to 0.2 MPa, more preferably 0.1 MPa to 0.15 MPa. The reaction temperature is preferably 250 to 600°C, more preferably 300 to 550°C, and even more preferably 330 to 500°C. The space velocity is preferably 300 to 10000 (1 / h), more preferably 400 to 8000 (1 / h), and even more preferably 500 to 6000 (1 / h).

[0067] (Acetone purification process) The method for producing isopropanol according to this disclosure may include a step of separating and / or purifying acetone (hereinafter also referred to as the acetone purification step).

[0068] The acetone purification process may be carried out by known gas-liquid separation methods, etc. For example, the composition obtained in the acetone production process may be separated (sometimes called gas-liquid separation) into a gas mainly composed of hydrogen or carbon dioxide and a liquid mixture mainly composed of acetone. The acetone purification process may also include a step of distilling acetone.

[0069] (Hydrogen purification process) The method for producing isopropanol according to this disclosure may include a hydrogen purification step (hereinafter also referred to as the hydrogen purification step). The hydrogen purification step is not particularly limited, but known methods such as physical absorption, chemical absorption, membrane separation, cryogenic separation, and compression liquefaction can be employed.

[0070] Physical absorption is a method of separating and recovering carbon dioxide from a mixed gas by physical action such as adsorption or dissolution without chemical reaction, and the PSA (Pressure Swing Adsorption) method is particularly preferred. Chemical absorption mainly involves reacting carbon dioxide with basic substances such as amines or alkalis to convert it into a form such as bicarbonate, which is then absorbed. By heating or reducing the pressure of the absorbent liquid in which carbon dioxide has been absorbed, the carbon dioxide is separated and recovered as a gas from the absorbent liquid. For membrane separation, a method using a separation membrane that selectively permeates hydrogen or carbon dioxide is preferred. The membrane used at this time is not particularly limited, but examples include polymer material membranes, dendrimer membranes, amine group-containing membranes, and zeolite membranes. The separation membrane may also contain metal atoms. The metal atoms are not particularly limited, but examples include Pd. These methods may be carried out one or more times. For example, after separating acetone from the composition obtained in the acetone production process, carbon dioxide may be separated from the composition containing hydrogen and carbon dioxide.

[0071] (Isopropanol purification process) The method for producing isopropanol according to this disclosure may include a step for purifying isopropanol. For example, if the composition obtained in the acetone hydrogenation step is a gas-liquid mixture containing gas, it may be separated into a gas mainly composed of, for example, hydrogen, and a liquid mixture containing isopropanol by a known gas-liquid separation method. Here, gas refers to a substance that exists as a gas under the pressurized and cooled conditions in the gas-liquid separation operation. In the isopropanol purification step, the pressure in the gas-liquid separation operation is preferably 0.1 MPa to 2 MPa, and more preferably 0.2 MPa to 1 MPa. In the isopropanol purification step, the temperature in the gas-liquid separation operation is preferably 0°C to 50°C, and more preferably 5°C to 40°C.

[0072] The purification process for isopropanol may include a distillation step. The distillation step may be carried out by, for example, thin-film distillation or rectification. It may be a continuous or batch process. The distillation step may be azeotropic distillation. Since isopropanol forms an azeotropic mixture with water, if the liquid mixture containing isopropanol contains water, high-purity isopropanol can be obtained by azeotropic distillation.

[0073] (Catalyst regeneration process) In the method for producing isopropanol according to this disclosure, if deterioration of 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 and regenerated.

[0074] <Examples of preferred forms of methods for producing isopropanol> The following (5) to (8) are examples of preferred embodiments of the method for producing isopropanol according to the present disclosure. (5) A method for producing isopropanol, comprising the steps of supplying a composition containing acetone and hydrogen to a reactor containing a catalyst comprising a metal element of Group 10 of the periodic table and a metal oxide having an acid strength (H0 constant) of +7.2 or higher, and hydrogenating the acetone. (6) A method for producing isopropanol according to (5), comprising a step of hydrogenating acetone at a reaction temperature of 20°C to 100°C. (7) A method for producing isopropanol according to either (5) or (6), wherein the catalyst is the acetone hydrogenation catalyst described in any of (1) to (4) above. (8) A method for producing isopropanol according to any one of (5) to (7), further comprising the acetone production step. [Examples]

[0075] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, "parts" means "parts by weight" and "%" means "mass%".

[0076] <Catalyst Synthesis> (Catalyst Preparation Example 1) 10% by mass Pt / ZrO2 5.4 g of dinitrodiammineplatinum nitrate solution (manufactured by Tanaka Kikinzoku Co., Ltd., Pt content 8.19% by mass) was weighed into a beaker. 4 g of ZrO2 powder (manufactured by Daiichi Kigenso Kagaku Co., Ltd., EP-L, specific surface area 10² m²) was placed in a magnetic dish. 2 The dinitrodiammineplatinic acid solution was added to the mixture (H0 constant +9.3 to +7.2) and then heated while stirring with a glass rod to evaporate the water. The resulting powder was dried at 120°C for 10 hours and then calcined at 400°C for 1 hour to prepare catalyst 1. The composition of the obtained catalyst 1 was 10% Pt / ZrO2 by mass.

[0077] (Catalyst Preparation Example 2) 10% by mass Pt / SiO2 In catalyst preparation example 1, ZrO2 was replaced with SiO2 (Carriact Q-50C manufactured by Fuji Silysia Chemical Co., Ltd., specific surface area 70 m²). 2 Catalyst 2 was prepared in the same manner as in Catalyst Preparation Example 1, except that the concentration ( / g) and H0 constant (+6.8 to +3.3) were changed. The composition of the obtained catalyst 1 was 10 mass% Pt / SiO2.

[0078] (Catalyst Preparation Example 3) 10% by mass Ru / SiO2 Catalyst 3 was prepared in the same manner as in Catalyst Preparation Example 1, except that 5.4 g of dinitrodiammineplatinum nitric acid solution was replaced with 11.3 g of ruthenium nitrate solution (manufactured by Tanaka Kikinzoku Co., Ltd., Ru content 3.92% by mass). The composition of the obtained catalyst 3 was 10% by mass Ru / SiO2.

[0079] (Catalyst Preparation Example 4) 20% by mass Cu / SiO2 Catalyst 4 was prepared in the same manner as in Catalyst Preparation Example 1, except that 5.4 g of dinitrodiammineplatinic acid solution was replaced with 3.8 g of copper nitrate trihydrate (Nacalai Tesque, special grade). The composition of the obtained catalyst 4 was 20% by mass Cu / SiO2.

[0080] (Catalyst Preparation Example 5) 60% by mass CuO / 30% by mass ZnO / 10% by mass Al2O3 30 g of copper nitrate trihydrate (Nacalai Tesque, special grade), 18 g of zinc nitrate hexahydrate (Nacalai Tesque, special grade), and 12.1 g of aluminum nitrate hexahydrate (Nacalai Tesque, special grade) were dissolved in 300 mL of pure water (Solution A). 52.5 g of sodium carbonate (Nacalai Tesque, special grade) was dissolved in 300 mL of pure water (Solution B). Solutions A and B were added dropwise at a constant rate to a beaker containing 750 mL of pure water at room temperature under stirring to form a precipitate. The resulting precipitate was filtered and washed with water, then dried at 120 °C for 10 hours and calcined at 300 °C for 4 hours to prepare catalyst 5. The composition of the obtained catalyst 5 was 60% CuO / 30% ZnO / 10% Al2O3.

[0081] (Catalyst Preparation Example 6) 1% by mass Pt / ZrO2 Catalyst 6 was prepared in the same manner as in Catalyst Preparation Example 1, except that the amount of dinitrodiammineplatinic acid solution was changed from 5.4 g to 0.49 g. The composition of the obtained catalyst 6 was 1 mass% Pt / ZrO2.

[0082] (Catalyst Preparation Example 7) 1% by mass Pt / CeO2 In Catalyst Preparation Example 1, 5.4 g of dinitrodiammineplatinic acid solution was reduced to 0.49 g, and ZrO2 was replaced with CeO2 (3CO, manufactured by Rhodia, with a specific surface area of ​​171 m²). 2 Catalyst 7 was prepared in the same manner as in Catalyst Preparation Example 1, except that the indicator changed only at H0 constants of +7.2 and +7.2 (no range specified). The composition of the obtained catalyst 7 was 1 mass% Pt / CeO2.

[0083] (Catalyst Preparation Example 8) 1% by mass Pt / Al2O3 In Catalyst Preparation Example 1, except that 5.4 g of dinitrodiammineplatinum nitrate solution was changed to 0.49 g and ZrO2 was changed to Al2O3 (NGa-150 manufactured by Sasol, specific surface area 150 m 2 / g, H0 constant +6.8 to +3.3), Catalyst 8 was prepared in the same manner as in Catalyst Preparation Example 1. The composition of the obtained Catalyst 8 was 1% by mass Pt / Al2O3.

[0084] (Catalyst Preparation Example 9) 1% by mass Pt / TiO2 In Catalyst Preparation Example 1, except that 5.4 g of dinitrodiammineplatinum nitrate solution was changed to 0.49 g and ZrO2 was changed to TiO2 (DT-51 manufactured by Crystal Global, specific surface area 64 m 2 / g, H0 constant +6.8 to +1.5), Catalyst 9 was prepared in the same manner as in Catalyst Preparation Example 1. The composition of the obtained Catalyst 9 was 1% by mass Pt / TiO2.

[0085] (Catalyst Preparation Example 10) 1% by mass Pt / NaY In Catalyst Preparation Example 1, except that 5.4 g of dinitrodiammineplatinum nitrate solution was changed to 0.49 g and ZrO2 was changed to NaY-type zeolite (manufactured by Tosoh Corporation, "HSZ-320NAA", specific surface area 766 m 2 / g, H0 constant +6.8 to -3.0), Catalyst 10 was prepared in the same manner as in Catalyst Preparation Example 1. The composition of the obtained Catalyst 10 was 1% by mass Pt / NaY. (Catalyst Preparation Example 11) 1% by mass Ru / CeO2 In Catalyst Preparation Example 1, 5.4 g of dinitrodiammineplatinum nitrate solution was changed to 1.0 g of ruthenium nitrate solution (Ru content 3.92% by mass manufactured by Tanaka Kikinzoku Kogyo K.K.), and ZrO2 was changed to CeO2 (3CO manufactured by Rhodia, specific surface area 171 m 2 / g, H0 constant +7.2 / Since the indicator changed only at +7.2, no range is specified), Catalyst 11 was prepared in the same manner as in Catalyst Preparation Example 1. The composition of the obtained Catalyst 11 was 1% by mass Ru / CeO2.

[0086]

Table 1

[0087] <Acetone Hydrogenation> (Example 1) Catalyst 1 (0.7g) was packed into a stainless steel fixed-bed flow reactor, and nitrogen (N2) 2.5cm³ was added. 3 / min (flow rate at standard conditions: 0°C, 1 atm) and hydrogen (H2) 15cm³ 3 Pretreatment was carried out at 300°C for 1 hour while flowing 1 / min (at standard conditions: 0°C, 1 atm). Next, after setting the reaction temperature, acetone (Nacalai Tesque, special grade) was supplied at a rate of 19.14 mg / min to the heating section on the catalyst layer inlet side using a microsyringe feeder. The acetone was vaporized and supplied to the catalyst layer, thereby initiating the isopropanol production reaction by acetone hydrogenation. The reactor outlet gas was introduced into a trap placed in an ice bath, where unreacted raw materials and products were collected. The liquid components collected in the trap were quantitatively analyzed using GC-FID (Agilent 7890B / capillary column HP-plot Q). Gaseous products not collected in the trap were directly introduced into GC-FID and analyzed. From these analytical results, the acetone conversion rate and isopropanol selectivity were calculated using the following formulas. The reaction results obtained at an electric furnace temperature of 60°C are shown in Table 2. Conversion rate (%) = 100 - (Outlet acetone molar flow rate / Inlet acetone molar flow rate) Selectivity (%) = 100 × [Molar flow rate of generated isopropanol / (Molar flow rate of inlet acetone × conversion rate)]

[0088] (Comparative Example 1) The isopropanol production reaction by acetone hydrogenation was carried out in the same manner as in Example 1, except that catalyst 1 was replaced with catalyst 2. The reaction results obtained at an electric furnace temperature of 100°C are shown in Table 2.

[0089] (Comparative Example 2) The isopropanol production reaction by acetone hydrogenation was carried out in the same manner as in Example 1, except that catalyst 1 was replaced with catalyst 3. The reaction results obtained at an electric furnace temperature of 100°C are shown in Table 2.

[0090] (Comparative Example 3) The isopropanol production reaction by acetone hydrogenation was carried out in the same manner as in Example 1, except that catalyst 1 was replaced with catalyst 4. The reaction results obtained at an electric furnace temperature of 100°C are shown in Table 2.

[0091] (Comparative Example 4) The isopropanol production reaction by acetone hydrogenation was carried out in the same manner as in Example 1, except that catalyst 1 was replaced with catalyst 5. The reaction results obtained at electric furnace temperatures of 80 and 100°C are shown in Table 2.

[0092] [Table 2]

[0093] Comparing the reaction results at 100°C using 10% by mass Pt / SiO2 (Comparative Example 1), 10% by mass Ru / SiO2 (Comparative Example 2), and 20% by mass Cu / SiO2 (Comparative Example 3), all prepared with SiO2 as a support, it was found that the conversion rate was high with the Pt catalyst, indicating that Pt has superior acetone hydrogenation activity among these active metals. Furthermore, when catalyst 1, in which Pt was supported on ZrO2 with an H0 constant of +9.3 to +7.2 (Example 1), an acetone conversion rate of 99.2% and an isopropanol selectivity of 99.4% were obtained at an electric furnace temperature of 60°C. The 60 mass% CuO-30 mass% ZnO-10 mass% Al2O3 catalyst (Comparative Example 4) showed higher activity than the catalysts in Comparative Examples 1-3, with a conversion rate of 93.5% at 100°C. However, at 80°C, the conversion rate was 47%, indicating lower activity compared to the 10 mass% Pt / ZrO2 catalyst.

[0094] (Example 2) Catalyst 6 (0.7g) was packed into a stainless steel fixed-bed flow reactor, and nitrogen (N2) was supplied at 55cm³. 3 / min (flow rate at standard conditions: 0°C, 1 atm) and hydrogen (H2) 30cm³ 3Pretreatment was carried out at 300°C for 1 hour while flowing 1 minute (at standard conditions: 0°C, 1 atm). Next, after setting the reaction temperature, acetone (Nacalai Tesque, special grade) was supplied at a rate of 40.45 mg / min to the heating section on the catalyst layer inlet side using a microsyringe feeder. The acetone was vaporized and supplied to the catalyst layer to start the isopropanol production reaction by acetone hydrogenation. Analysis of the reactor outlet components was carried out in the same manner as in Example 1. Table 3 shows the results when the reaction was carried out at room temperature without electric furnace heating, and the results when the reaction was carried out at 45°C.

[0095] (Example 3) The isopropanol production reaction by acetone hydrogenation was carried out in the same manner as in Example 2, except that catalyst 6 was replaced with catalyst 7. The reaction results obtained at room temperature and at an electric furnace temperature of 50°C are shown in Table 3.

[0096] (Comparative Example 5) The isopropanol production reaction by acetone hydrogenation was carried out in the same manner as in Example 2, except that catalyst 6 was replaced with catalyst 8. The reaction results obtained at room temperature and at an electric furnace temperature of 45°C are shown in Table 3.

[0097] (Comparative Example 6) The isopropanol production reaction by acetone hydrogenation was carried out in the same manner as in Example 2, except that catalyst 6 was replaced with catalyst 9. The reaction results obtained at room temperature and at an electric furnace temperature of 60°C are shown in Table 3.

[0098] (Comparative Example 7) The isopropanol production reaction by acetone hydrogenation was carried out in the same manner as in Example 2, except that catalyst 6 was replaced with catalyst 10. The reaction results obtained at room temperature are shown in Table 3.

[0099] (Comparative Example 8) The isopropanol production reaction by acetone hydrogenation was carried out in the same manner as in Example 2, except that catalyst 6 was replaced with catalyst 11. The reaction results obtained at room temperature are shown in Table 3.

[0100] [Table 3]

[0101] In catalysts 6-10, in which the support component was changed while the Pt load was 1% by mass, catalysts 6 and 7 of the present invention showed that the acetone hydrogenation reaction proceeded even at room temperature, resulting in a high conversion rate (Examples 2 and 3). At this time, the exothermic reaction caused by the acetone hydrogenation reaction increased the catalyst layer temperature, and the average catalyst layer temperature, calculated from the minimum and maximum temperatures of the catalyst layer, could be maintained at 45-47°C, higher than room temperature (24-28°C), without external heating by an electric furnace. Although some acetone hydrogenation also proceeded in catalyst 8 (Comparative Example 5), the activity was insufficient compared to Examples 2 and 3. When the Pt in the high-performance 1% by mass Pt / CeO2 (catalyst 6) was replaced with Ru (Comparative Example 8), the acetone hydrogenation reaction hardly proceeded at around room temperature.

[0102] From the above, it has become clear that the catalyst of this disclosure exhibits high activity in the hydrogenation of acetone and can produce isopropanol even in low-temperature ranges, for example, without external heating.

[0103] The catalyst of this invention can effectively promote the acetone hydrogenation reaction even at low temperatures near room temperature. Therefore, it is possible to carry out the reaction autonomously using the heat generated by the reaction without external heat supply. Furthermore, the acetone hydrogenation reaction is a reaction that is greatly affected by equilibrium, and low temperature and high pressure conditions are advantageous for avoiding equilibrium. Therefore, a catalyst that is active at lower temperatures is desirable. Since the catalyst of this invention shows high activity from around room temperature, it is very useful from the viewpoint of avoiding equilibrium constraints.

Claims

1. Metal elements in Group 10 of the periodic table and acid strength (H ０ An acetone hydrogenation catalyst comprising a metal oxide whose constant is +7.2 or greater.

2. The acetone hydrogenation catalyst according to claim 1, wherein the content of the metal element of Group 10 of the periodic table is 0.1 to 10% by mass.

3. The acetone hydrogenation catalyst according to claim 1 or 2, wherein the metal oxide is zirconium oxide and / or cerium oxide.

4. The acetone hydrogenation catalyst according to claim 1 or 2, wherein the metal element of Group 10 of the periodic table is platinum.

5. A composition containing acetone and hydrogen is used with a metal element from Group 10 of the periodic table and an acid strength (H ０ A method for producing isopropanol, comprising the steps of supplying a catalyst containing a metal oxide having a constant of +7.2 or higher to a reactor, and hydrogenating acetone.

6. A method for producing isopropanol according to claim 5, comprising a step of hydrogenating acetone at a reaction temperature of 20°C to 100°C.

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