Methods for producing alcohol

Abstract

The present invention provides a method for producing alcohol that can improve reactivity while suppressing the formation of by-products. [Solution] A method for producing alcohol, comprising a hydrogenation step in which a raw material carboxylic acid and hydrogen gas are reacted in the presence of a catalyst (A) containing Co, Fe, and Zr to obtain an alcohol.

Description

Technical Field

[0001] The present invention relates to a method for producing alcohol.

Background Art

[0002] As a method for producing alcohol, a method of catalytic hydrogenation of fatty acid esters is generally known and widely used industrially. On the other hand, attempts have been made to catalytically hydrogenate free fatty acids in the presence of a catalyst to obtain alcohol.

[0003] For example, Patent Document 1 discloses a method for producing alcohol by hydrogenating a carboxylic acid under high-pressure conditions in the presence of a Co catalyst containing one or more elements selected from Zr, Y, La, Ce, Si, Al, Sc, V, and Mo.

[0004] Patent Document 2 discloses a method for producing aliphatic alcohol by hydrogenating a fatty acid or fatty acid ester under high-pressure conditions in the presence of a catalyst in which a catalytic metal containing one or more elements selected from Co and Cu is supported on a carrier.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0006] The method for producing alcohol disclosed in Patent Document 1 is said to have high catalytic activity and be industrially satisfactory, and the method for producing aliphatic alcohol disclosed in Patent Document 2 is said to suppress the formation of by-products such as hydrocarbons and is industrially satisfactory. However, there was room for improvement in the method for producing alcohol from the viewpoint of suppressing the formation of by-products while improving reactivity.

[0007] Therefore, the object of the present invention is to provide a method for producing alcohol that can suppress the formation of by-products while improving reactivity. [Means for solving the problem]

[0008] The inventors have found that the above problem can be solved by reacting a starting carboxylic acid with hydrogen gas in the presence of a catalyst (A) containing specific components (Co, Fe, Zr). In other words, the present invention provides the following [1] and [2]. [1] A method for producing an alcohol, comprising a hydrogenation step of reacting a starting carboxylic acid with hydrogen gas in the presence of a catalyst (A) containing Co, Fe, and Zr to obtain an alcohol. [2] A catalyst (A) containing Co, Fe, and Zr, used in a method for producing alcohols using a carboxylic acid as a raw material, wherein the Fe content in the catalyst (A) is 0.1 moles or more and 30 moles or less per 100 moles of Co. [Effects of the Invention]

[0009] The present invention provides a method for producing alcohol that can suppress the formation of by-products while improving reactivity. [Modes for carrying out the invention]

[0010] The present invention provides a method for producing alcohol, comprising a hydrogenation step in which a carboxylic acid and hydrogen gas are reacted in the presence of a catalyst (A) containing Co, Fe, and Zr to obtain an alcohol.

[0011] According to the present invention, the effect is to suppress the generation of by-products while improving reactivity. The reason for this is not entirely clear, but it can be considered as follows: When Fe is used as a co-catalyst for Co and Zr, some or all of the Co and Fe alloy together, resulting in an optimal catalyst surface structure. Furthermore, the Zr compound further disperses the Co and Fe, significantly improving reactivity. As a result, it is believed that when catalyst (A) is used in a method for producing alcohols using carboxylic acids as raw materials, the reactivity can be improved while suppressing the formation of by-products compared to conventional catalysts.

[0012] [Catalyst (A)] The present invention's method for producing alcohol uses a catalyst (A) containing specific components (Co, Fe, Zr). The Co, Fe, and Zr contained in catalyst (A) may be oxides.

[0013] The Fe content in catalyst (A) is preferably 0.01 moles or more, more preferably 0.05 moles or more, even more preferably 0.1 moles or more, and even more preferably 1 mole or more per 100 moles of Co, and preferably 60 moles or less, more preferably 40 moles or less, even more preferably 30 moles or less, even more preferably 20 moles or less, and even more preferably 15 moles or less, from the viewpoint of improving reactivity and suppressing the formation of by-products. The Fe content in catalyst (A) can be specifically determined by measurement using the method described in the examples.

[0014] The Zr content in catalyst (A) is preferably 1 mole or more, more preferably 5 moles or more, even more preferably 10 moles or more, and preferably 40 moles or less, more preferably 30 moles or less, and even more preferably 25 moles or less, per 100 moles of Co, from the viewpoint of improving reactivity and suppressing the formation of by-products. The Zr content in catalyst (A) can be specifically determined by measurement using the method described in the examples.

[0015] By including Fe and Zr together with Co in catalyst (A), the effects of the present invention are obtained, which include improving reactivity while suppressing the formation of by-products.

[0016] In the alcohol production method of the present invention, a catalyst (A) containing specific components (Co, Fe, Zr) is used, but a catalyst (A) in which Co, Fe, and Zr are supported on a carrier may also be used. The support for catalyst (A) is not particularly limited as long as it can support specific components (Co, Fe, Zr). From the viewpoint of improving catalytic activity and selectivity, suitable supports for catalyst (A) include diatomaceous earth, alumina, silica, silica-alumina, magnesia, zirconia, titania, ceria, activated carbon, and composite oxides thereof. Furthermore, if the support for catalyst (A) is zirconia, even if catalyst (A) contains only two components, Co and Fe, it will still be considered catalyst (A) of the present invention. If catalyst (A) contains a support, the amount of support in catalyst (A) is preferably 80% by mass or less, more preferably 50% by mass or less, and even more preferably 30% by mass or less. The shape of the carrier is not particularly limited, and is usually a powder with a median diameter (d50) of typically 1 to 300 μm, but other shapes derived from the powder may be used as needed.

[0017] Catalyst (A) may contain other metal components besides the specific components (Co, Fe, Zr), as long as they do not impair the effects of the present invention. Other metal components that can be used to improve catalytic activity and selectivity include, for example, Na, Mg, Al, Si, P, K, Ca, Sc, Ti, V, Mn, Ni, Cu, Zn, Ga, Ge, Sr, Y, Nb, No, Ru, Rh, Pd, Ag, In, Sn, Cs, Ba, W, Re, Ir, Pt, Au, Bi, La, and Ce.

[0018] The content of other metal components in catalyst (A) is preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 3% by mass or less, and even more preferably 0% by mass.

[0019] The shape of the catalyst (A) is not particularly limited, and examples thereof include powder, granules, noodles, and pellets. In addition, the shapes of granules, noodles, pellets, etc. can be produced by granulating and molding the powdered catalyst (A) by a known method.

[0020] [Method for Producing Catalyst (A)] The catalyst (A) used in the present invention can be produced by (i) preparing a catalyst precursor and (ii) subjecting the catalyst precursor to a reduction treatment. Further, it is preferable to perform an oxidation stabilization treatment for forming an oxide film on the surface of the catalyst (A) to stabilize it.

[0021] (i) Preparation of Catalyst Precursor The catalyst precursor can be prepared by a well-known method such as a coprecipitation method, a physical mixing method, an impregnation support method, etc. From the viewpoint of ease of manufacturing the catalyst, the coprecipitation method is preferably used for the preparation of the catalyst precursor.

[0022] The coprecipitation method is a method of mixing an aqueous mixed solution of metal salts and a precipitant. The method for preparing the catalyst precursor by the coprecipitation method can be carried out, for example, by the method shown below. An aqueous mixed solution of metal salts of Co, Fe, and Zr respectively and an aqueous solution of a precipitant are stirred and mixed at room temperature (25 °C). After the completion of the stirring and mixing, the resulting precipitate is washed with water and then dried at a predetermined temperature and time. Thereafter, calcination is performed at a predetermined temperature and time to obtain a catalyst precursor.

[0023] Here, the atomic ratio of Co to Fe to Zr (Co / Fe / Zr) in the prepared catalyst precursor is considered to be the same as the atomic ratio of Co to Fe to Zr (Co / Fe / Zr) in the produced catalyst (A). Therefore, the suitable ranges of the contents of Fe and Zr respectively with respect to 100 moles of Co in the catalyst precursor are the same as the suitable ranges of the contents of Fe and Zr respectively with respect to 100 moles of Co in the above-mentioned catalyst (A). The atomic ratio (Co / Fe / Zr) of Co, Fe, and Zr contained in the mixed aqueous solution of metal salts can be appropriately adjusted based on the preparation examples described in the examples.

[0024] The mass ratio of the mixed aqueous solution of metal salts to the aqueous solution of the precipitant (mixed aqueous solution of metal salts: aqueous solution of precipitant) is usually 1:0.3 to 1.0, and preferably 1:0.5 to 0.6.

[0025] When the mass ratio of the mixed aqueous solution of metal salts to the aqueous solution of precipitant is, for example, 1:0.5 to 0.6, the concentration of the mixed aqueous solution of metal salts is preferably 0.1 mol / L or higher, more preferably 0.5 mol / L or higher, even more preferably 1.0 mol / L or higher, and preferably 5.0 mol / L or lower, more preferably 3.0 mol / L or lower, and even more preferably 2.0 mol / L or lower, from the viewpoint of improving catalyst yield and catalytic activity.

[0026] When the mass ratio of the mixed aqueous solution of the metal salt to the aqueous solution of the precipitant is, for example, 1:0.5 to 0.6, the concentration of the aqueous solution of the precipitant is preferably 0.5 mol / L or higher, more preferably 1.0 mol / L or higher, even more preferably 2.0 mol / L or higher, and preferably 5.0 mol / L or lower, more preferably 4.0 mol / L or lower, and even more preferably 3.0 mol / L or lower, from the viewpoint of improving catalyst yield and catalytic activity.

[0027] Examples of metal salts of Co, Fe, and Zr include nitrates, sulfates, chlorides, ammonium complex salts, acetates, oxalates, and acetylacetonates. From the viewpoint of ease of catalyst production, it is preferable that the metal salts of Co, Fe, and Zr be at least one selected from the group consisting of nitrates, sulfates, and chlorides.

[0028] Examples of precipitating agents include ammonia, urea, ammonium carbonate, sodium bicarbonate, sodium carbonate, sodium hydroxide, and potassium hydroxide. From the viewpoint of not leaving any impurities in the catalyst, the precipitating agent is preferably at least one selected from the group consisting of ammonium carbonate, ammonia, and urea.

[0029] From the viewpoint of improving catalytic activity, the drying temperature of the precipitate after washing with water is preferably 30°C or higher, more preferably 50°C or higher, even more preferably 80°C or higher, and preferably 180°C or lower, more preferably 150°C or lower, and even more preferably 120°C or lower. From the viewpoint of improving catalytic activity, the drying time of the precipitate after washing with water is preferably 1 hour or more, more preferably 5 hours or more, even more preferably 10 hours or more, and preferably 48 hours or less, more preferably 36 hours or less, and even more preferably 24 hours or less.

[0030] From the viewpoint of improving catalytic activity, the calcination temperature of the precipitate after drying is preferably 200°C or higher, more preferably 250°C or higher, even more preferably 300°C or higher, and preferably 800°C or lower, more preferably 600°C or lower, and even more preferably 500°C or lower.

[0031] From the viewpoint of improving catalytic activity, the calcination time of the precipitate after drying is preferably 1 hour or more, more preferably 2 hours or more, even more preferably 3 hours or more, and preferably 10 hours or less, more preferably 8 hours or less, and even more preferably 6 hours or less.

[0032] (ii) Reduction treatment of catalyst precursor From the viewpoint of catalyst activation, it is preferable to treat the catalyst precursor with a reducing agent. The reduction treatment can be carried out by applying a predetermined amount of reducing agent to the catalyst precursor, and then flowing the gas phase containing the reducing agent through it at a predetermined supply rate, temperature, and time. The reduction treatment of the catalyst precursor can be carried out in a flow system or in a closed system.

[0033] Examples of reducing agents include hydrogen, carbon monoxide, formaldehyde, sodium borohydride, and hydrazine. However, from the viewpoint of ease of catalytic reduction treatment, it is preferable to use at least one selected from the group consisting of hydrogen and carbon monoxide, with hydrogen being more preferable. When hydrogen is used as a reducing agent, it may be used alone or mixed with other gases. Examples of other gases include inert gases (e.g., nitrogen) and water vapor.

[0034] In the reduction treatment of the catalyst precursor, it is preferable to pass the reducing agent through a gas phase system over the catalyst precursor in a dry state, but it is also possible to pass the reducing agent through a liquid phase system while the catalyst precursor is impregnated in a liquid. Examples of liquids used to impregnate the catalyst precursor include hydrocarbons such as liquid paraffin, aliphatic alcohols, aliphatic esters, and carboxylic acids that serve as hydrogenation raw materials.

[0035] From the viewpoint of improving reduction efficiency, the concentration of the reducing agent in the gas phase is preferably 0.1% by volume or more, more preferably 0.5% by volume or more, even more preferably 1% by volume or more, and even more preferably 2% by volume or more. From the viewpoint of suppressing a rapid reduction reaction, it is preferably 100% by volume or less, more preferably 50% by volume or less, and even more preferably 10% by volume or less.

[0036] The amount of gas phase containing the reducing agent supplied is appropriately determined according to the reaction scale, but for example, when the reaction scale is 14 L, from the viewpoint of improving catalytic activity, it is preferably 0.1 L / min or more, more preferably 0.5 L / min or more, even more preferably 1 L / min or more, and preferably 30 L / min or less, more preferably 20 L / min or less, and even more preferably 10 L / min or less.

[0037] From the viewpoint of improving catalytic activity, the reduction treatment temperature is preferably 300°C or higher, more preferably 350°C or higher, even more preferably 400°C or higher, and preferably 900°C or lower, more preferably 800°C or lower, and even more preferably 600°C or lower.

[0038] From the viewpoint of improving catalytic activity, the reduction treatment time is preferably 1 hour or more, more preferably 5 hours or more, even more preferably 10 hours or more, and preferably 48 hours or less, more preferably 36 hours or less, and even more preferably 24 hours or less.

[0039] (iii) Oxidation stabilization treatment of catalyst (A) Since catalyst (A), obtained by reduction treatment, may react violently with oxygen in the air and generate heat if exposed to air as is, it is preferable to perform an oxidation stabilization treatment on the surface of catalyst (A) to stabilize it by forming an oxide film. The oxidation stabilization treatment is a process performed in the gas phase, and can be carried out by flowing the gas phase containing the oxygen at a predetermined supply rate, temperature, and time relative to the catalyst (A), with the oxygen concentration in the gas phase being set to a predetermined amount. The oxidation stabilization treatment of catalyst (A) may be carried out in a flow system or in a closed system.

[0040] Oxygen may be used alone, or it may be used in mixture with other gases. Other gases include inert gases (e.g., nitrogen) and air.

[0041] From the viewpoint of promoting the oxidation reaction, the oxygen concentration in the gas phase is preferably 0.01% by volume or more, more preferably 0.1% by volume or more, and even more preferably 0.5% by volume or more. From the viewpoint of suppressing a rapid reaction, it is preferably 100% by volume or less, more preferably 50% by volume or less, and even more preferably 10% by volume or less.

[0042] The amount of oxygen-containing gaseous phase supplied is appropriately determined according to the reaction scale, but for example, when the reaction scale is 14 L, from the viewpoint of allowing the oxidation reaction to proceed at an appropriate rate, it is preferably 0.01 L / min or more, more preferably 0.1 L / min or more, even more preferably 0.2 L / min or more, and preferably 5 L / min or less, more preferably 2 L / min or less, and even more preferably 1 L / min or less.

[0043] The oxidation stabilization treatment temperature is preferably 5°C or higher, more preferably 15°C or higher, even more preferably 20°C or higher, and preferably 50°C or lower, more preferably 40°C or lower, and even more preferably 30°C or lower, from the viewpoint of allowing the oxidation reaction to proceed at an appropriate rate.

[0044] The oxidation stabilization treatment time is preferably 1 hour or more, more preferably 3 hours or more, even more preferably 5 hours or more, and preferably 20 hours or less, more preferably 15 hours or less, and even more preferably 10 hours or less, from the viewpoint of the progress of the oxidation reaction.

[0045] [Method of producing alcohol] The present invention provides a method for producing alcohol, which includes a hydrogenation step in which a raw material carboxylic acid is reacted with hydrogen gas in the presence of a catalyst (A) containing Co, Fe, and Zr to obtain an alcohol. Furthermore, in the alcohol production method of the present invention, it is preferable to perform a pretreatment step to reduce the oxide film of catalyst (A) that has been oxidatively stabilized in (iii) above, before the hydrogenation step.

[0046] [Carboxylic acid] In the present invention's method for producing alcohol, a carboxylic acid is used as a raw material. Examples of carboxylic acids used in the present invention include aliphatic carboxylic acids, aromatic carboxylic acids, alicyclic carboxylic acids, dibasic acids (dicarboxylic acids), and polycarboxylic acids. Among these, from the viewpoint of obtaining useful alcohols, aliphatic carboxylic acids having 8 to 24 carbon atoms are preferred, and aliphatic carboxylic acids having 8 to 22 carbon atoms are more preferred.

[0047] Examples of aliphatic carboxylic acids include saturated fatty acids such as acetic acid (C2), propionic acid (C3), butyric acid (C4), isobutyric acid (C4), valeric acid (C5), caproic acid (C6), caprylic acid (C8), capric acid (C10), lauric acid (C12), myristic acid (C14), palmitic acid (C16), stearic acid (C18), isostearic acid (C18), arachidic acid (C20), behenic acid (C22), lignoceric acid (C24), cervic acid (C26), montanic acid (C28), and melalisic acid (C30); and unsaturated fatty acids such as maleic acid (C4), fumaric acid (C4), and oleic acid (C18).

[0048] Examples of aromatic carboxylic acids include benzoic acid (C7) and phthalic acid (C8).

[0049] Examples of dibasic acids (dicarboxylic acids) include oxalic acid (C2), malonic acid (C3), succinic acid (C4), glutaric acid (C5), adipic acid (C6), azelaic acid (C7), phthalic acid (C8), sebacic acid (C10), maleic acid (C4), and fumaric acid (C4).

[0050] Examples of alicyclic carboxylic acids include cyclopentanecarboxylic acid (C6) and cyclohexanecarboxylic acid (C7).

[0051] The carboxylic acid used in this invention may have functional groups other than a carboxyl group. Other functional groups besides carboxyl groups include amino groups, carbonyl groups, hydroxyl groups, sulfonic acid groups, phosphonic acid groups, alkoxy groups, and halo groups.

[0052] (Step 1) Pre-treatment process The pretreatment step preferably involves adding a dispersion medium to the catalyst (A) that has been oxidatively stabilized in (iii) above, and performing a reduction treatment in the liquid phase in the presence of a reducing agent, while stirring the liquid phase under predetermined conditions at predetermined pressure, temperature, and time. The liquid phase may contain water. The reduction treatment of catalyst (A) can be carried out in a flow system or in a closed system. It is preferable to perform a dehydration treatment under predetermined conditions after the reduction treatment of catalyst (A).

[0053] Examples of reducing agents include hydrogen, carbon monoxide, formaldehyde, sodium borohydride, and hydrazine. However, from the viewpoint of not leaving impurities in the container, it is preferable to use at least one selected from the group consisting of hydrogen and carbon monoxide, with hydrogen being more preferable. When hydrogen is used as a reducing agent, it may be used alone or mixed with other gases. Examples of other gases include inert gases (e.g., nitrogen) and water vapor.

[0054] From the viewpoint of improving productivity, the dispersion medium used in the reduction process is preferably the same alcohol as the product intended for production.

[0055] The peripheral speed of the stirring blade in the reduction process is appropriately determined according to the reaction scale, but for example, when the reaction scale is 0.5 L, from the viewpoint of improving reduction efficiency, it is preferably 10 m / min or more, more preferably 40 m / min or more, even more preferably 60 m / min or more, and preferably 250 m / min or less, more preferably 190 m / min or less, and even more preferably 130 m / min or less.

[0056] The reduction treatment pressure (gauge pressure) is preferably 1.0 MPaG or higher, more preferably 2.0 MPaG or higher, even more preferably 5.0 MPaG or higher, and preferably 30 MPaG or lower, more preferably 20 MPaG or lower, and even more preferably 10 MPaG or lower, from the viewpoint of improving catalytic activity.

[0057] From the viewpoint of improving catalytic activity, the reduction treatment temperature is preferably 80°C or higher, more preferably 100°C or higher, even more preferably 150°C or higher, and preferably 300°C or lower, more preferably 250°C or lower, and even more preferably 200°C or lower.

[0058] From the viewpoint of improving catalytic activity, the reduction treatment time is preferably 1 hour or more, more preferably 2 hours or more, even more preferably 3 hours or more, and preferably 20 hours or less, more preferably 15 hours or less, and even more preferably 10 hours or less.

[0059] The dehydration treatment after the reduction treatment of catalyst (A) is preferably carried out in the presence of an inert gas (e.g., nitrogen). The amount of inert gas supplied is determined appropriately according to the reaction scale, but for example, if the reaction scale is 0.5 L, from the viewpoint of improving dewatering efficiency, it is preferably 0.1 NL / min or more, more preferably 0.5 NL / min or more, even more preferably 1 NL / min or more, and preferably 10 NL / min or less, more preferably 7 NL / min or less, and even more preferably 5 NL / min or less.

[0060] The peripheral speed of the stirring blade in the dehydration treatment after the reduction treatment of catalyst (A) is appropriately determined according to the reaction scale. For example, when the reaction scale is 0.5 L, from the viewpoint of improving dehydration efficiency, it is preferably 10 m / min or more, more preferably 40 m / min or more, even more preferably 60 m / min or more, and preferably 250 m / min or less, more preferably 190 m / min or less, and even more preferably 130 m / min or less.

[0061] The dehydration pressure (gauge pressure) after the reduction treatment of catalyst (A) is preferably 0.01 MPaG or higher, more preferably 0.08 MPaG or higher, even more preferably 0.1 MPaG or higher, and preferably 10 MPaG or lower, more preferably 8 MPaG or lower, and even more preferably 5 MPaG or lower, from the viewpoint of improving dehydration properties.

[0062] From the viewpoint of improving dehydration properties, the dehydration temperature after the reduction treatment of catalyst (A) is preferably 70°C or higher, more preferably 90°C or higher, even more preferably 130°C or higher, and preferably 280°C or lower, more preferably 230°C or lower, and even more preferably 180°C or lower.

[0063] From the viewpoint of improving dehydration properties, the dehydration treatment time after the reduction treatment of catalyst (A) is preferably 0.2 hours or more, more preferably 0.3 hours or more, even more preferably 0.5 hours or more, and preferably 10 hours or less, more preferably 5 hours or less, and even more preferably 2 hours or less.

[0064] (Step 2) Hydrogenation process In the hydrogenation step, it is preferable to replace the gas phase with hydrogen gas in the presence of catalyst (A) that has gone through step (1) above, and to carry out the hydrogenation reaction with the raw material carboxylic acid and hydrogen gas in the liquid phase at a predetermined pressure, temperature, and time while stirring the liquid phase under predetermined conditions. The hydrogenation reaction can be carried out in a flow system or a closed system.

[0065] The hydrogenation reaction can be either a suspension-bed reaction or a fixed-bed reaction, and the appropriate method can be selected depending on the catalytic activity, reaction scale, etc. The reaction format of the alcohol production method of the present invention may be batch, semi-batch, or continuous. When the hydrogenation reaction is a suspension bed reaction, a batch or semi-batch reaction is preferred from the viewpoint of operability, and the amount of catalyst (A) is preferably 1.0 part by mass or more, more preferably 2.0 parts by mass or more, and even more preferably 5.0 parts by mass or more, per 100 parts by mass of raw material carboxylic acid, from the viewpoint of improving the yield of alcohol, and preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less, from the viewpoint of economics. When the hydrogenation reaction is a fixed-bed reaction, a continuous reaction is preferred from the viewpoint of improving the yield of alcohol. In the case of a continuous reaction, the LHSV (liquid space velocity) is preferably 20 / hr or less, more preferably 10 / hr or less, even more preferably 5 / hr or less, and even more preferably 3 / hr or less, from the viewpoint of improving the yield of alcohol, and preferably 0.1 / hr or more, more preferably 0.2 / hr or more, even more preferably 0.5 / hr or more, and even more preferably 1 / hr or more, from the viewpoint of improving productivity.

[0066] The amount of hydrogen gas supplied is determined appropriately according to the reaction scale, but for example, when the reaction scale is 0.5 L, from the viewpoint of improving the alcohol yield, it is preferably 0.1 NL / min or more, more preferably 0.5 NL / min or more, even more preferably 1 NL / min or more, and preferably 10 NL / min or less, more preferably 5 NL / min or less, and even more preferably 3 NL / min or less.

[0067] The peripheral speed of the stirring blade is appropriately determined according to the reaction scale, but for example, when the reaction scale is 0.5 L, from the viewpoint of reaction rate, it is preferably 10 m / min or more, more preferably 40 m / min or more, even more preferably 60 m / min or more, and preferably 250 m / min or less, more preferably 190 m / min or less, and even more preferably 130 m / min or less.

[0068] The reaction pressure (gauge pressure) in the hydrogenation process is preferably 1.0 MPaG or higher, more preferably 2.0 MPaG or higher, even more preferably 5.0 MPaG or higher, and preferably 30 MPaG or lower, more preferably 20 MPaG or lower, and even more preferably 10 MPaG or lower, from the viewpoint of improving alcohol yield and economic efficiency.

[0069] The reaction temperature in the hydrogenation step is appropriately determined considering the boiling point of the starting carboxylic acid, but from the viewpoint of improving the yield of alcohol, it is preferably 80°C or higher, more preferably 100°C or higher, even more preferably 150°C or higher, and even more preferably 180°C or higher, and preferably 300°C or lower, more preferably 280°C or lower, and even more preferably 240°C or lower.

[0070] The reaction time in the hydrogenation step is appropriately determined according to the amount of catalyst (A), reaction pressure, and reaction temperature. When the reaction is batch-type, from the viewpoint of improving the yield of alcohol, it is usually 1 hour or more, and from the viewpoint of productivity, it is preferably 3 hours or less, more preferably 2 hours or less. When the reaction is continuous, the LHSV (liquid space velocity) is preferably 20 / hr or less, more preferably 10 / hr or less, even more preferably 5 / hr or less, and even more preferably 3 / hr or less, from the viewpoint of improving the yield of alcohol, and preferably 0.1 / hr or more, more preferably 0.2 / hr or more, even more preferably 0.5 / hr or more, and even more preferably 1 / hr or more, from the viewpoint of productivity.

[0071] The alcohol produced by the manufacturing method of the present invention depends on the type of starting material carboxylic acid used, but may be saturated or unsaturated, primary or secondary, or have a cyclic structure. Furthermore, from the viewpoint of improving the yield of alcohol, the number of carbon atoms in the alcohol produced by the manufacturing method of the present invention is preferably 8 or more, more preferably 9 or more, even more preferably 10 or more, and preferably 36 or less, more preferably 22 or less, even more preferably 20 or less, and even more preferably 18 or less.

[0072] The manufacturing method of the present invention makes it possible to suppress the formation of by-products while improving reactivity. The alcohol obtained by the manufacturing method of the present invention can be used as is for various purposes, but it can also be purified by distillation or other operations as needed. The alcohol is useful as a raw material or intermediate raw material for surfactants, cosmetics, fragrances, plasticizers, lubricants, etc.

[0073] In addition to the embodiments described above, the present invention discloses the following method for producing alcohol. <1> A method for producing an alcohol, comprising a hydrogenation step in which a starting carboxylic acid is reacted with hydrogen gas in the presence of a catalyst (A) containing Co, Fe, and Zr to obtain an alcohol. <2> The Fe content in the catalyst (A) is preferably 0.01 moles or more, more preferably 0.05 moles or more, even more preferably 0.1 moles or more, and even more preferably 1 mole or more, per 100 moles of Co, and preferably 60 moles or less, more preferably 40 moles or less, even more preferably 30 moles or less, even more preferably 20 moles or less, and even more preferably 15 moles or less. <1> The method for producing alcohol as described above. <3> The reaction temperature of the hydrogenation step is preferably 80°C or higher, more preferably 100°C or higher, even more preferably 150°C or higher, and even more preferably 180°C or higher, and preferably 300°C or lower, more preferably 280°C or lower, and even more preferably 240°C or lower. <1> or <2> The method for producing alcohol as described above. <4> The Fe content in the catalyst (A) is preferably 0.01 moles or more, and preferably 60 moles or less, per 100 moles of Co, and The reaction temperature of the hydrogenation step is preferably 80°C or higher, and preferably 300°C or lower. <1> The method for producing alcohol as described above. <5> The Fe content in the catalyst (A) is more preferably 0.05 moles or more, and more preferably 40 moles or less, per 100 moles of Co, and The reaction temperature of the hydrogenation step is more preferably 100°C or higher, and more preferably 280°C or lower. <1> The method for producing alcohol as described above. <6> The Fe content in the catalyst (A) is more preferably 0.1 moles or more, and more preferably 30 moles or less, per 100 moles of Co, and The reaction temperature of the hydrogenation step is more preferably 150°C or higher, and more preferably 240°C or lower. <1> The method for producing alcohol as described above. <7> The Fe content in the catalyst (A) is more preferably 1 mole or more, and more preferably 20 moles or less, per 100 moles of Co, and The reaction temperature of the hydrogenation step is more preferably 180°C or higher, and even more preferably 240°C or lower. <1> The method for producing alcohol as described above. <8> The Fe content in the catalyst (A) is more preferably 1 mole or more, and more preferably 15 moles or less, per 100 moles of Co, and The reaction temperature of the hydrogenation step is more preferably 180°C or higher, and even more preferably 240°C or lower. <1> The method for producing alcohol as described above. <9> The reaction pressure (gauge pressure) of the hydrogenation step is preferably 1.0 MPaG or higher, more preferably 2.0 MPaG or higher, even more preferably 5.0 MPaG or higher, and preferably 30 MPaG or lower, more preferably 20 MPaG or lower, and even more preferably 10 MPaG or lower. <1> ~ <8> A method for producing alcohol as described in any of the following. <10> The Fe content in the catalyst (A) is preferably 0.01 moles or more, and preferably 60 moles or less, per 100 moles of Co. The reaction temperature of the hydrogenation step is preferably 80°C or higher, and preferably 300°C or lower, The reaction pressure (gauge pressure) of the hydrogenation step is preferably 1.0 MPaG or higher, and preferably 30 MPaG or lower. <1> ~ <8> A method for producing alcohol as described in any of the following. <11> The Fe content in the catalyst (A) is more preferably 0.05 moles or more, and more preferably 40 moles or less, per 100 moles of Co. The reaction temperature of the hydrogenation step is more preferably 100°C or higher, and more preferably 280°C or lower, The reaction pressure (gauge pressure) of the hydrogenation step is more preferably 2.0 MPaG or higher, and more preferably 20 MPaG or lower. <1> ~ <8> A method for producing alcohol as described in any of the following. <12> The Fe content in the catalyst (A) is more preferably 0.1 moles or more, and more preferably 30 moles or less, per 100 moles of Co. The reaction temperature of the hydrogenation step is more preferably 150°C or higher, and more preferably 240°C or lower, The reaction pressure (gauge pressure) of the hydrogenation step is more preferably 5.0 MPaG or higher, and more preferably 10 MPaG or lower. <1> ~ <8> A method for producing alcohol as described in any of the following. <13> The Fe content in the catalyst (A) is more preferably 1 mole or more, and more preferably 20 moles or less, per 100 moles of Co. The reaction temperature of the hydrogenation step is more preferably 180°C or higher, and even more preferably 240°C or lower, The reaction pressure (gauge pressure) of the hydrogenation step is more preferably 5.0 MPaG or higher, and more preferably 10 MPaG or lower. <1> ~ <8> A method for producing alcohol as described in any of the following. <14> The Fe content in the catalyst (A) is more preferably 1 mole or more, and more preferably 15 moles or less, per 100 moles of Co. The reaction temperature of the hydrogenation step is more preferably 180°C or higher, and even more preferably 240°C or lower, The reaction pressure (gauge pressure) of the hydrogenation step is more preferably 5.0 MPaG or higher, and more preferably 10 MPaG or lower. <1> ~ <8> A method for producing alcohol as described in any of the following. <15> The Zr content in the catalyst (A) is preferably 1 mole or more, more preferably 5 moles or more, even more preferably 10 moles or more, and preferably 40 moles or less, more preferably 30 moles or less, and even more preferably 25 moles or less, per 100 moles of Co. <1> ~ <14> A method for producing alcohol as described in any of the following. <16> The Fe content in the catalyst (A) is preferably 0.01 moles or more, and preferably 60 moles or less, per 100 moles of Co. The Zr content in the catalyst (A) is preferably 1 mole or more, and preferably 40 moles or less, per 100 moles of Co. The reaction temperature of the hydrogenation step is preferably 80°C or higher, and preferably 300°C or lower, The reaction pressure (gauge pressure) of the hydrogenation step is preferably 1.0 MPaG or higher, and preferably 30 MPaG or lower. <1> ~ <14> A method for producing alcohol as described in any of the following. <17> The Fe content in the catalyst (A) is more preferably 0.05 moles or more, and more preferably 40 moles or less, per 100 moles of Co. The Zr content in the catalyst (A) is more preferably 5 moles or more, and more preferably 30 moles or less, per 100 moles of Co. The reaction temperature of the hydrogenation step is more preferably 100°C or higher, and more preferably 280°C or lower, The reaction pressure (gauge pressure) of the hydrogenation step is more preferably 2.0 MPaG or higher, and more preferably 20 MPaG or lower. <1> ~ <14> A method for producing alcohol as described in any of the following. <18> The Fe content in the catalyst (A) is more preferably 0.1 moles or more, and more preferably 30 moles or less, per 100 moles of Co. The Zr content in the catalyst (A) is more preferably 10 moles or more, and more preferably 25 moles or less, per 100 moles of Co. The reaction temperature of the hydrogenation step is more preferably 150°C or higher, and more preferably 240°C or lower, The reaction pressure (gauge pressure) of the hydrogenation step is more preferably 5.0 MPaG or higher, and more preferably 10 MPaG or lower. <1> ~ <14> A method for producing alcohol as described in any of the following. <19> The Fe content in the catalyst (A) is more preferably 1 mole or more, and more preferably 20 moles or less, per 100 moles of Co. The Zr content in the catalyst (A) is more preferably 10 moles or more, and more preferably 25 moles or less, per 100 moles of Co. The reaction temperature of the hydrogenation step is more preferably 180°C or higher, and even more preferably 240°C or lower, The reaction pressure (gauge pressure) of the hydrogenation step is more preferably 5.0 MPaG or higher, and more preferably 10 MPaG or lower. <1> ~ <14> A method for producing alcohol as described in any of the following. <20> The Fe content in the catalyst (A) is more preferably 1 mole or more, and more preferably 15 moles or less, per 100 moles of Co. The Zr content in the catalyst (A) is more preferably 10 moles or more, and more preferably 25 moles or less, per 100 moles of Co. The reaction temperature of the hydrogenation step is more preferably 180°C or higher, and even more preferably 240°C or lower, The reaction pressure (gauge pressure) of the hydrogenation step is more preferably 5.0 MPaG or higher, and more preferably 10 MPaG or lower. <1> ~ <14> A method for producing alcohol as described in any of the following. <a1> A method for producing the catalyst (A), comprising the following steps (i) and (ii). Step (i) A step of preparing a catalyst precursor, comprising stirring and mixing a mixed aqueous solution of metal salts of Co, Fe, and Zr with an aqueous solution of a precipitant, and after stirring and mixing is complete, washing the precipitate formed by aging with water and then drying it. Step (ii) A step of reducing the catalyst precursor obtained in step (i). <a2> The reduction treatment temperature in step (ii) is preferably 300°C or higher, more preferably 350°C or higher, even more preferably 400°C or higher, and preferably 900°C or lower, more preferably 800°C or lower, and even more preferably 600°C or lower. <a1>A method for producing the catalyst (A) described above. <a3> Step (i) comprises a step of further firing after drying, wherein the firing temperature of the firing step is preferably 200°C or higher, more preferably 250°C or higher, even more preferably 300°C or higher, and preferably 800°C or lower, more preferably 600°C or lower, and even more preferably 500°C or lower. <a1>or <a2>A method for producing the catalyst (A) described above. <a4> Step (i) includes a step of further firing after drying, and the firing temperature in this firing step is 200°C or more and 600°C or less. The reduction treatment temperature in step (ii) is between 400°C and 600°C. <a1>or <a2>A method for producing the catalyst (A) described above. <a5> Step (ii) is a step in which a reducing agent is circulated in a gas phase system and a reduction treatment is performed, The concentration of the reducing agent in the gas phase is preferably 0.1% by volume or more, more preferably 0.5% by volume or more, even more preferably 1% by volume or more, and even more preferably 2% by volume or more, and preferably 100% by volume or less, more preferably 50% by volume or less, and even more preferably 10% by volume or less. <a1> ~ <a4>A method for producing the catalyst (A) as described in any of the above. <a6> Step (i) includes a step of further firing after drying, and the firing temperature in this firing step is 200°C or more and 600°C or less. Step (ii) is a step in which a reducing agent is circulated in a gas phase system and a reduction treatment is performed, The reducing agent concentration in the gas phase is between 2% by volume and 10% by volume. The reduction treatment temperature is between 400°C and 600°C. <a1> ~ <a4>A method for producing the catalyst (A) as described in any of the above. <a7> The reduction treatment time in step (ii) is preferably 1 hour or more, more preferably 5 hours or more, even more preferably 10 hours or more, and preferably 48 hours or less, more preferably 36 hours or less, and even more preferably 24 hours or less. <a1> ~ <a6>A method for producing the catalyst (A) as described in any of the above. <a8> Step (i) includes a step of further firing after drying, and the firing temperature in this firing step is 200°C or more and 600°C or less. Step (ii) is a step in which a reducing agent is circulated in a gas phase system and a reduction treatment is performed, The reducing agent concentration in the gas phase is between 2% by volume and 10% by volume. The reduction treatment temperature is between 400°C and 600°C. The reduction treatment time is between 10 and 36 hours. <a1> ~ <a7>A method for producing the catalyst (A) as described in any of the above. <a9> The precipitating agent in step (i) is at least one selected from the group consisting of ammonia, urea, ammonium carbonate, sodium bicarbonate, sodium carbonate, sodium hydroxide, and potassium hydroxide, and preferably at least one selected from the group consisting of ammonium carbonate, ammonia, and urea. <a1> ~ <a8>A method for producing the catalyst (A) as described in any of the above. <a10> The precipitant in step (i) is ammonium carbonate. Step (i) includes a step of further firing after drying, and the firing temperature in this firing step is 200°C or more and 600°C or less. Step (ii) is a step in which a reducing agent is circulated in a gas phase system and a reduction treatment is performed, The reducing agent concentration in the gas phase is between 2% by volume and 10% by volume. The reduction treatment temperature is between 400°C and 600°C. The reduction treatment time is between 10 and 36 hours. <a1> ~ <a9>A method for producing the catalyst (A) as described in any of the above. <a11> In step (i), each of the metal salts of Co, Fe, and Zr is at least one selected from the group consisting of nitrates, sulfates, chlorides, ammonium complex salts, acetates, oxalates, and acetylacetonate salts, preferably at least one selected from the group consisting of nitrates, sulfates, and chlorides. <a1> ~ <a10>A method for producing the catalyst (A) as described in any of the above. <a12> In step (i), the metal salts of Co, Fe, and Zr are nitrates. The precipitant in step (i) is ammonium carbonate. Step (i) includes a step of further firing after drying, and the firing temperature in this firing step is 200°C or more and 600°C or less. Step (ii) is a step in which a reducing agent is circulated in a gas phase system and a reduction treatment is performed, The reducing agent concentration in the gas phase is between 2% by volume and 10% by volume. The reduction treatment temperature is between 400°C and 600°C. The reduction treatment time is between 10 and 36 hours. <a1> ~ <a11>A method for producing the catalyst (A) as described in any of the above. <a13> Furthermore, the following step (iii) is performed: <a1> ~ <a12>A method for producing the catalyst (A) described above. Step (iii) Oxidation stabilization process to form an oxide film on the surface of catalyst (A) and stabilize it. <a14> In step (iii), the oxidation stabilization treatment temperature is preferably 5°C or higher, more preferably 15°C or higher, even more preferably 20°C or higher, and preferably 50°C or lower, more preferably 40°C or lower, and even more preferably 30°C or lower. <a13>A method for producing the catalyst (A) described above. <a15> In step (i), the metal salts of Co, Fe, and Zr are nitrates. The precipitant in step (i) is ammonium carbonate. Step (i) includes a step of further firing after drying, and the firing temperature in this firing step is 200°C or more and 600°C or less. Step (ii) is a step in which a reducing agent is circulated in a gas phase system and a reduction treatment is performed, The reducing agent concentration in the gas phase is between 2% by volume and 10% by volume. The reduction treatment temperature is between 400°C and 600°C. The reduction treatment time is between 10 hours and 36 hours. In step (iii), the oxidation stabilization treatment temperature is between 15°C and 40°C. <a13>or <a14>A method for producing the catalyst (A) described above. <a16> The oxidation stabilization treatment step (iii) is performed in the gas phase, and the oxygen concentration in the gas phase is preferably 0.01% by volume or more, more preferably 0.1% by volume or more, even more preferably 0.5% by volume or more, and preferably 100% by volume or less, more preferably 50% by volume or less, and even more preferably 10% by volume or less. <a13> ~ <a15>A method for producing the catalyst (A) as described in any of the above. <a17> In step (i), the metal salts of Co, Fe, and Zr are nitrates. The precipitant in step (i) is ammonium carbonate. Step (i) includes a step of further firing after drying, and the firing temperature in this firing step is 200°C or more and 600°C or less. Step (ii) is a step in which a reducing agent is circulated in a gas phase system and a reduction treatment is performed, The reducing agent concentration in the gas phase is between 2% by volume and 10% by volume. The reduction treatment temperature is between 400°C and 600°C. The reduction treatment time is between 10 hours and 36 hours. In step (iii), the oxidation stabilization treatment temperature is 15°C or higher and 40°C or lower. The oxidation stabilization process in step (iii) is a process performed in the gas phase. The oxygen concentration in the gas phase is between 0.5% by volume and 10% by volume. <a13> ~ <a16>A method for producing the catalyst (A) as described in any of the above. <a18> In step (iii), the oxidation stabilization treatment time is preferably 1 hour or more, more preferably 3 hours or more, even more preferably 5 hours or more, and preferably 20 hours or less, more preferably 15 hours or less, and even more preferably 10 hours or less. <a13> ~ <a17>A method for producing the catalyst (A) as described in any of the above. <a19> In step (i), the metal salts of Co, Fe, and Zr are nitrates. The precipitant in step (i) is ammonium carbonate. Step (i) includes a step of further firing after drying, and the firing temperature in this firing step is 200°C or more and 600°C or less. Step (ii) is a step in which a reducing agent is circulated in a gas phase system and a reduction treatment is performed, The reducing agent concentration in the gas phase is between 2% by volume and 10% by volume. The reduction treatment temperature is between 400°C and 600°C. The reduction treatment time is between 10 hours and 36 hours. In step (iii), the oxidation stabilization treatment temperature is 15°C or higher and 40°C or lower. The oxidation stabilization treatment time is between 5 and 10 hours. The oxidation stabilization process in step (iii) is a process performed in the gas phase. The oxygen concentration in the gas phase is between 0.5% by volume and 10% by volume. <a13> ~ <a18>A method for producing the catalyst (A) as described in any of the above. <a20> In step (i), the drying time of the precipitate after washing is preferably 1 hour or more, more preferably 5 hours or more, even more preferably 10 hours or more, and preferably 48 hours or less, more preferably 36 hours or less, and even more preferably 24 hours or less. <a1> ~ <a19>A method for producing the catalyst (A) as described in any of the above. <a21> In step (i), the metal salts of Co, Fe, and Zr are nitrates. The precipitant in step (i) is ammonium carbonate. In step (i), the drying time of the precipitate after washing is between 10 and 24 hours. Step (i) includes a step of further firing after drying, and the firing temperature in this firing step is 200°C or more and 600°C or less. Step (ii) is a step in which a reducing agent is circulated in a gas phase system and a reduction treatment is performed, The reducing agent concentration in the gas phase is between 2% by volume and 10% by volume. The reduction treatment temperature is between 400°C and 600°C. The reduction treatment time is between 10 hours and 36 hours. In step (iii), the oxidation stabilization treatment temperature is 15°C or higher and 40°C or lower. The oxidation stabilization treatment time is between 5 and 10 hours. The oxidation stabilization process in step (iii) is a process performed in the gas phase. The oxygen concentration in the gas phase is between 0.5% by volume and 10% by volume. <a13> ~ <a20>A method for producing the catalyst (A) as described in any of the above. <a22> In step (i), the drying temperature of the precipitate after washing is preferably 30°C or higher, more preferably 50°C or higher, even more preferably 80°C or higher, and preferably 180°C or lower, more preferably 150°C or lower, and even more preferably 120°C or lower. <a1> ~ <a21>A method for producing the catalyst (A) as described in any of the above. <a23> The precipitant in step (i) is ammonium carbonate. In step (i), the metal salts of Co, Fe, and Zr are nitrates. In step (i), the drying time of the precipitate after washing is between 10 and 24 hours. The drying temperature of the precipitate after washing is between 80°C and 120°C. Step (i) includes a step of further firing after drying, and the firing temperature in this firing step is 200°C or more and 600°C or less. Step (ii) is a step in which a reducing agent is circulated in a gas phase system and a reduction treatment is performed, The reducing agent concentration in the gas phase is between 2% by volume and 10% by volume. The reduction treatment temperature is between 400°C and 600°C. The reduction treatment time is between 10 hours and 36 hours. In step (iii), the oxidation stabilization treatment temperature is 15°C or higher and 40°C or lower. The oxidation stabilization treatment time is between 5 and 10 hours. The oxidation stabilization process in step (iii) is a process performed in the gas phase. The oxygen concentration in the gas phase is between 0.5% by volume and 10% by volume. <a13> ~ <a22>A method for producing the catalyst (A) as described in any of the above. <a24> Step (i) comprises a step of further calcination after drying, wherein the calcination time of the dried precipitate is preferably 1 hour or more, more preferably 2 hours or more, even more preferably 3 hours or more, and preferably 10 hours or less, more preferably 8 hours or less, and even more preferably 6 hours or less. <a1> ~ <a23>A method for producing the catalyst (A) as described in any of the above. <a25> In step (i), the metal salts of Co, Fe, and Zr are nitrates. The precipitant in step (i) is ammonium carbonate. In step (i), the drying time of the precipitate after washing is between 10 and 24 hours. The drying temperature of the precipitate after washing is between 80°C and 120°C. Step (i) includes a step of further firing after drying, and the firing temperature in this firing step is 200°C or more and 600°C or less. The baking time is between 3 and 6 hours. Step (ii) is a step in which a reducing agent is circulated in a gas phase system and a reduction treatment is performed, The reducing agent concentration in the gas phase is between 2% by volume and 10% by volume. The reduction treatment temperature is between 400°C and 600°C. The reduction treatment time is between 10 hours and 36 hours. In step (iii), the oxidation stabilization treatment temperature is 15°C or higher and 40°C or lower. The oxidation stabilization treatment time is between 5 and 10 hours. The oxidation stabilization process in step (iii) is a process performed in the gas phase. The oxygen concentration in the gas phase is between 0.5% by volume and 10% by volume. <a13> ~ <a24>A method for producing the catalyst (A) as described in any of the above. <21> <a1> ~ <a25>The method for producing catalyst (A) described in any of the above includes a hydrogenation step in which a catalyst (A) containing Co, Fe, and Zr is produced, and then a raw material carboxylic acid is reacted with hydrogen gas in the presence of the obtained catalyst (A) to obtain an alcohol. <1> ~ <20> A method for producing alcohol as described in any of the following. <22> <a1> ~ <a25>After producing a catalyst (A) containing Co, Fe, and Zr by a method for producing catalyst (A) as described in any of the above, The process includes a hydrogenation step in which a raw material carboxylic acid and hydrogen gas are reacted in the presence of a catalyst (A) that has undergone the following pretreatment step (step 1) to obtain an alcohol. <1> ~ <20> A method for producing alcohol as described in any of the following. Pre-treatment step (Step 1) <a1> ~ <a25>A process of mixing catalyst (A) obtained by a method for producing catalyst (A) as described in any of the above with a dispersion medium, performing a reduction treatment in the liquid phase in the presence of a reducing agent, and preferably performing a dehydration treatment after the reduction treatment. <23> In the aforementioned pretreatment step (step 1), the pressure (gauge pressure) of the reduction treatment is preferably 1.0 MPaG or higher, more preferably 2.0 MPaG or higher, even more preferably 5.0 MPaG or higher, and preferably 30 MPaG or lower, more preferably 20 MPaG or lower, and even more preferably 10 MPaG or lower. <22> The method for producing alcohol as described above. <24> The Fe content in the catalyst (A) is more preferably 1 mole or more, and more preferably 15 moles or less, per 100 moles of Co. The Zr content in the catalyst (A) is more preferably 10 moles or more, and more preferably 25 moles or less, per 100 moles of Co. The reaction temperature of the hydrogenation step is more preferably 180°C or higher, and even more preferably 240°C or lower, The reaction pressure (gauge pressure) of the hydrogenation step is more preferably 5.0 MPaG or higher, and more preferably 10 MPaG or lower. The aforementioned <a25>After producing catalyst (A) containing Co, Fe, and Zr by the method for producing catalyst (A) described above, a pretreatment step (step 1) is performed. In the pretreatment step (step 1), the pressure (gauge pressure) of the reduction treatment is preferably 5.0 MPaG or more and 10 MPaG or less. <22> The method for producing alcohol as described above. <25> In the aforementioned pretreatment step (step 1), the reduction treatment time is preferably 1 hour or more, more preferably 2 hours or more, even more preferably 3 hours or more, and preferably 20 hours or less, more preferably 15 hours or less, and even more preferably 10 hours or less. <22> ~ <24> A method for producing alcohol as described in any of the following. <26> The Fe content in the catalyst (A) is more preferably 1 mole or more, and more preferably 15 moles or less, per 100 moles of Co. The Zr content in the catalyst (A) is more preferably 10 moles or more, and more preferably 25 moles or less, per 100 moles of Co. The reaction temperature of the hydrogenation step is more preferably 180°C or higher, and even more preferably 240°C or lower, The reaction pressure (gauge pressure) of the hydrogenation step is more preferably 5.0 MPaG or higher, and more preferably 10 MPaG or lower. The aforementioned <a25>After producing catalyst (A) containing Co, Fe, and Zr by the method for producing catalyst (A) described above, a pretreatment step (step 1) is performed. In the pretreatment step (step 1), the pressure (gauge pressure) of the reduction treatment is 5.0 MPaG or more and 10 MPaG or less. The reduction treatment time is between 3 and 10 hours. <22> ~ <25> A method for producing alcohol as described in any of the following. <27> The Fe content in the catalyst (A) is more preferably 1 mole or more, and more preferably 15 moles or less, per 100 moles of Co. The Zr content in the catalyst (A) is more preferably 10 moles or more, and more preferably 25 moles or less, per 100 moles of Co. The hydrogenation reaction is a suspension bed reaction. The reaction temperature of the hydrogenation step is more preferably 180°C or higher, and even more preferably 240°C or lower, The reaction pressure (gauge pressure) of the hydrogenation step is more preferably 5.0 MPaG or higher, and more preferably 10 MPaG or lower. The aforementioned <a25>After producing catalyst (A) containing Co, Fe, and Zr by the method for producing catalyst (A) described above, a pretreatment step (step 1) is performed. In the pretreatment step (step 1), the pressure (gauge pressure) of the reduction treatment is 5.0 MPaG or more and 10 MPaG or less. The reduction treatment time is between 3 and 10 hours. <22> ~ <26> A method for producing alcohol as described in any of the following. <28> The aforementioned raw material carboxylic acid is an aliphatic carboxylic acid having 8 to 24 carbon atoms. <1> ~ <27> A method for producing alcohol as described in any of the following. <29> The aforementioned raw material carboxylic acid is an aliphatic carboxylic acid having 8 to 22 carbon atoms. <1> ~ <27> A method for producing alcohol as described in any of the following. <30> The Fe content in the catalyst (A) is more preferably 1 mole or more, and more preferably 15 moles or less, per 100 moles of Co. The Zr content in the catalyst (A) is more preferably 10 moles or more, and more preferably 25 moles or less, per 100 moles of Co. The aforementioned raw material carboxylic acid is an aliphatic carboxylic acid having 8 to 22 carbon atoms. The hydrogenation reaction in the aforementioned hydrogenation step is a suspension bed reaction. The reaction temperature of the hydrogenation step is more preferably 180°C or higher, and even more preferably 240°C or lower, The reaction pressure (gauge pressure) of the hydrogenation step is more preferably 5.0 MPaG or higher, and more preferably 10 MPaG or lower. The aforementioned <a25>After producing catalyst (A) containing Co, Fe, and Zr by the method for producing catalyst (A) described above, a pretreatment step (step 1) is performed. In the pretreatment step (step 1), the pressure (gauge pressure) of the reduction treatment is 5.0 MPaG or more and 10 MPaG or less. The reduction treatment time is between 3 and 10 hours. <22> ~ <29> A method for producing alcohol as described in any of the following. <31> The dispersion medium in the aforementioned pretreatment step (step 1) is the same alcohol as the one intended for production. <22> ~ <30> A method for producing alcohol as described in any of the following. <32> The Fe content in the catalyst (A) is more preferably 1 mole or more, and more preferably 15 moles or less, per 100 moles of Co. The Zr content in the catalyst (A) is more preferably 10 moles or more, and more preferably 25 moles or less, per 100 moles of Co. The aforementioned raw material carboxylic acid is an aliphatic carboxylic acid having 8 to 22 carbon atoms. The hydrogenation reaction in the aforementioned hydrogenation step is a suspension bed reaction. The reaction temperature of the hydrogenation step is more preferably 180°C or higher, and even more preferably 240°C or lower, The reaction pressure (gauge pressure) of the hydrogenation step is more preferably 5.0 MPaG or higher, and more preferably 10 MPaG or lower. The aforementioned <a25>After producing catalyst (A) containing Co, Fe, and Zr by the method for producing catalyst (A) described above, a pretreatment step (step 1) is performed. In the pretreatment step (step 1), the dispersion medium is the same alcohol as the product intended for production. The pressure (gauge pressure) for the reduction treatment is between 5.0 MPaG and 10 MPaG. The reduction treatment time is between 3 and 10 hours. <22> ~ <31> A method for producing alcohol as described in any of the following. <33> The hydrogenation reaction is a suspension bed reaction, and the amount of catalyst (A) is preferably 1.0 part by mass or more, more preferably 2.0 parts by mass or more, even more preferably 5.0 parts by mass or more, and preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less, per 100 parts by mass of the raw material carboxylic acid. <1> ~ <32> A method for producing alcohol as described in any of the following. <34> The Fe content in the catalyst (A) is more preferably 1 mole or more, and more preferably 15 moles or less, per 100 moles of Co. The Zr content in the catalyst (A) is more preferably 10 moles or more, and more preferably 25 moles or less, per 100 moles of Co. The aforementioned raw material carboxylic acid is an aliphatic carboxylic acid having 8 to 22 carbon atoms. The hydrogenation reaction in the aforementioned hydrogenation step is a suspension bed reaction. The amount of catalyst (A) is 1.0 part by mass or more and 15 parts by mass or less per 100 parts by mass of the raw material carboxylic acid. The reaction temperature of the hydrogenation step is more preferably 180°C or higher, and even more preferably 240°C or lower, The reaction pressure (gauge pressure) of the hydrogenation step is more preferably 5.0 MPaG or higher, and more preferably 10 MPaG or lower. The aforementioned <a25>After producing the catalyst (A) containing Co, Fe, and Zr by the method for producing the catalyst (A) described in [], the pretreatment step (Step 1) was carried out. In the pretreatment step (Step 1), the dispersion medium is the same alcohol as the production target. The pressure (gauge pressure) of the reduction treatment is 5.0 MPaG or more and 10 MPaG or less. The reduction treatment time is 3 hours or more and 10 hours or less, and it is the method for producing an alcohol described in any one of <22> to <33>. <35> A catalyst (A) containing Co, Fe, and Zr, which is used in the method for producing an alcohol using a carboxylic acid as a raw material, where the content of Fe in the catalyst (A) is 0.1 mol or more and 30 mol or less with respect to 100 mol of Co.

Example

[0074] Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples.

[0075] (1) Composition analysis of the reaction solution after the hydrogenation reaction Using the reaction solution after the hydrogenation reaction as a sample, 2 drops were taken with a 2 mL disposable pipette into a 10 mL sample vial, and 1 mL of the trimethylsilyl (TMS) reagent "TMSI-H" (manufactured by GL Sciences Inc.) was added thereto. Further, 1.5 mL of hexane was added for dilution, and gas chromatography (GC) analysis was performed on the filtrate after filtration with a membrane filter having a pore size of 0.2 μm under the following measurement conditions. <GC measurement conditions> · "Agilent-8890 GC system" (manufactured by Agilent Technologies) · Capillary column · "Ultra-Alloy UA-1 (MS / HT)" 15 m, film thickness 0.15 μm, inner diameter 0.25 mm · Temperature 60 °C (2 minutes) → 10 °C / min → 350 °C (2 minutes) · Split ratio 15, Inj temperature 300 °C, Det temperature 350 °C

[0076] Next, based on the GC chromatogram, the content of raw material lauric acid, lauryl laurate produced from raw material lauric acid, and by-products in the sample was calculated using the method described below. Here, "by-products" refers to n-undecane, n-dodecane, and n-dodecyl ether. <Method for calculating the content of by-products in a sample> Using a GC chromatogram, the area of ​​the peak for each component was determined, and the content of each component in the sample was calculated by converting it to the amount produced per 1 kg of sample, using a calibration curve created with the standard substances listed below. The sum of these content amounts for each component was then used to determine the amount of by-product produced. The following substances were used as standard materials: lauric acid "Lunac 2098" (manufactured by Kao Corporation), lauryl laurate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), n-undodecane (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), n-dodecane (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and n-dodecyl ether (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.).

[0077] (2) Quantitative analysis of elements contained in the catalyst precursor The elements (Co, Fe, Zr) contained in the catalyst precursor were quantified using the inductively coupled plasma atomic emission spectrometer "iCAP6000" (manufactured by Thermo Fisher Scientific). The molar amounts of Fe and Zr were determined by setting the molar amount of Co to 100, and the atomic ratio of Co to Fe to Zr (Co / Fe / Zr) was calculated.

[0078] (3) Method for calculating catalytic activity and selectivity Catalytic activity was defined as the sum of the rate of decrease in acid value derived from lauric acid and the rate of decrease in saponification value derived from lauryl laurate. A higher value of this rate of decrease indicates higher catalytic activity. • Rate of decrease in acid value [1 / h] =[(Calculated acid value from lauric acid + Calculated saponification value from lauryl laurate) at reaction time A - (Calculated acid value from lauric acid + Calculated saponification value from lauryl laurate) at reaction time B)] / (BA)(h) • Calculated acid value derived from lauric acid [mgKOH / g] =[Amount of lauric acid per gram of sample determined from GC measurement (mol / g) × Amount of KOH × 1000 (mgKOH / mol)] • Calculated saponification value from lauryl laurate [mgKOH / g] =[Amount of lauryl laurate per gram of sample determined from GC measurement (mol / g) × Amount of KOH × 1000 (mgKOH / mol)]

[0079] Furthermore, selectivity was defined as the sum of the formation rates of each by-product relative to the rate of decrease in acid value, with the amount of by-products produced being the sum of these rates. A smaller amount of by-products indicates a higher effect in suppressing by-product formation. • Amount of by-products produced [mmol, per 1 kg of sample] =[(rate of formation of n-undecane (mmol / kg / h) + rate of formation of n-dodecane (mmol / kg / h) + rate of formation of n-dodecyl ether (mmol / kg / h)) during reaction time A to B)] / [rate of decrease in acid value (1 / h) during reaction time A to B)] • Production rate of n-undecane (mmol / kg / h) =[(Amount of n-undecane per kg of sample determined from GC measurement (mmol / kg)) at reaction time B hours - (Amount of n-undecane per kg of sample determined from GC measurement (mmol / kg)) at reaction time A hours)] / (BA)(h) • Production rate of n-dodecane (mmol / kg / h) =[(Amount of n-dodecane per kg of sample determined from GC measurement (mmol / kg)) at reaction time B hours - (Amount of n-dodecane per kg of sample determined from GC measurement (mmol / kg)) at reaction time A hours)] / (BA)(h) • Production rate of n-dodecyl ether (mmol / kg / h) =[(Amount of n-dodecyl ether per 1 kg of sample determined from GC measurement (mmol / kg)) at reaction time B hours - (Amount of n-dodecyl ether per 1 kg of sample determined from GC measurement (mmol / kg)) at reaction time A hours)] / (BA)(h)

[0080] (4) Production of catalysts (Manufacturing Example 1) (i) Preparation of catalyst precursors A mixed aqueous solution of metal salts containing cobalt nitrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), iron nitrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and zirconium nitrate (manufactured by Daiichi Rare Elements Chemical Industry Co., Ltd.), with an atomic ratio of Co to Fe to Zr (Co / Fe / Zr) of 100 / 8 / 22 (concentration of metal salts in the aqueous solution: 1.5 mol / L), was mixed with an aqueous solution of ammonium carbonate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as a precipitant (concentration of ammonium carbonate in the aqueous solution: 2.5 mol / L) at room temperature (25°C) by stirring. The mixed aqueous solution of metal salts and the aqueous solution of ammonium carbonate were used in a mass ratio of 1:0.6. After stirring and mixing, the precipitate formed during maturation was thoroughly washed with water and then dried overnight at 110°C. Subsequently, it was calcined at 400°C for 4 hours to prepare catalyst precursor 1 (powder). In catalyst precursor 1, the atomic ratio of Co to Fe to Zr (Co / Fe / Zr) was 100 / 9 / 21.

[0081] (ii) Reduction treatment of catalyst precursor The prepared catalyst precursor 1 was placed on a firing dish and set in a 14L electric furnace capable of providing a reducing atmosphere. Hydrogen diluted with nitrogen (hydrogen concentration in the gas phase; 4 vol%) was supplied at a rate of 5 L / min under atmospheric pressure and the temperature was raised to 450°C. The catalyst precursor 1 was subjected to a reduction treatment until no hydrogen absorption was observed, thereby obtaining the reduced catalyst 1. The reduction treatment time was 24 hours. Next, the system was purged with nitrogen and cooled to room temperature.

[0082] (iii) Oxidation stabilization treatment of catalyst (A) To oxidatively stabilize the surface of the reduced catalyst 1, air diluted with nitrogen (oxygen concentration in the gas phase; 1 vol.%) was flowed at a rate of 0.5 L / min under atmospheric pressure at room temperature (25°C). Catalyst 1 was subjected to oxidation stabilization treatment until no oxygen absorption was observed, thereby obtaining oxidation-stabilized catalyst 1. The oxidation stabilization treatment time was 8 hours. The atomic ratio of Co to Fe to Zr (Co / Fe / Zr) in oxidatively stabilized catalyst 1 is considered to be the same as the atomic ratio of Co to Fe to Zr (Co / Fe / Zr) in catalyst precursor 1.

[0083] (Manufacturing example 2) Catalyst 2 (powder) was obtained in the same manner as in (i) preparation of the catalyst precursor, (ii) reduction treatment of the catalyst precursor, and (iii) oxidation stabilization treatment of catalyst (A) in Production Example 1, except that in (i) preparation of the catalyst precursor, catalyst 2 (powder) was prepared using a metal mixed aqueous solution with an atomic ratio of Co to Fe to Zr (Co / Fe / Zr) of 100 / 5 / 21. In catalyst precursor 2, the atomic ratio of Co to Fe to Zr (Co / Fe / Zr) was 100 / 5 / 17.

[0084] (Manufacturing Example 3) Except for (i) preparation of the catalyst precursor in Production Example 1, where catalyst precursor 3 (powder) was prepared using a mixed metal aqueous solution with an atomic ratio of Co to Fe to Zr (Co / Fe / Zr) of 100 / 3 / 21, and where the mixed aqueous solution of metal salts and the aqueous solution of ammonium carbonate were used in a mass ratio of 1:0.5, catalyst 3 (powder) was obtained in the same manner as in Production Example 1, with the exception of (i) preparation of the catalyst precursor, (ii) reduction treatment of the catalyst precursor, and (iii) oxidation stabilization treatment of catalyst (A). In catalyst precursor 3, the atomic ratio of Co to Fe to Zr (Co / Fe / Zr) was 100 / 3 / 19.

[0085] (Manufacturing example 4) Except for (i) preparation of the catalyst precursor in Production Example 1, where catalyst precursor 4 (powder) was prepared using a mixed metal aqueous solution with an atomic ratio of Co to Fe to Zr (Co / Fe / Zr) of 100 / 5 / 11, and where the mixed aqueous solution of metal salts and the aqueous solution of ammonium carbonate were used in a mass ratio of 1:0.5, catalyst 4 (powder) was obtained in the same manner as in Production Example 1, except for (i) preparation of the catalyst precursor, (ii) reduction treatment of the catalyst precursor, and (iii) oxidation stabilization treatment of catalyst (A). In catalyst precursor 4, the atomic ratio of Co to Fe to Zr (Co / Fe / Zr) was 100 / 5 / 11.

[0086] (Manufacturing example 5) Catalyst 5 (powder) was prepared in the same manner as in (i) preparation of the catalyst precursor, (ii) reduction treatment of the catalyst precursor, and (iii) oxidation stabilization treatment of catalyst (A) in Production Example 1, except that in (i) preparation of the catalyst precursor, the atomic ratio of Co to Fe to Zr (Co / Fe / Zr) was 100 / 5 / 16, and a mixed aqueous solution of metal salts of cobalt nitrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), iron nitrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and zirconium nitrate (manufactured by Daiichi Rare Elements Chemical Industry Co., Ltd.) was used (concentration of metal salt in aqueous solution: 1.4 mol / L). In catalyst precursor 5, the atomic ratio of Co to Fe to Zr (Co / Fe / Zr) was 100 / 5 / 15.

[0087] (Manufacturing example 6) Catalyst 6 (powder) was obtained in the same manner as in (i) preparation of the catalyst precursor, (ii) reduction treatment of the catalyst precursor, and (iii) oxidation stabilization treatment of catalyst (A) in Production Example 1, except that in (i) preparation of the catalyst precursor, catalyst 6 (powder) was prepared using a metal mixed aqueous solution in which the atomic ratio of Co to Fe to Zr (Co / Fe / Zr) was 100 / 11 / 22. In catalyst precursor 6, the atomic ratio of Co to Fe to Zr (Co / Fe / Zr) was 100 / 11 / 19.

[0088] (Comparative manufacturing example 1) Catalyst 7 (powder) was obtained in the same manner as in (i) preparation of the catalyst precursor, (ii) reduction treatment of the catalyst precursor, and (iii) oxidation stabilization treatment of catalyst (A) in Production Example 1, except that in (i) preparation of the catalyst precursor, the catalyst precursor 7 (powder) was prepared using a metal mixed aqueous solution with an atomic ratio of Co to Fe to Zr (Co / Fe / Zr) of 100 / 0 / 20. In catalyst precursor 7, the atomic ratio of Co to Fe to Zr (Co / Fe / Zr) was 100 / 0 / 18.

[0089] Example 1 (Step 1) Pre-treatment process 192.9 g of lauryl alcohol "Calcol 2098" (manufactured by Kao Corporation), 5.6 g of deionized water, and 1.0 g of catalyst 1 (equivalent weight of catalyst precursor 1 prepared in (i) above), which had been oxidized and stabilized in (iii) above, were packed into a 500 mL autoclave. After replacing the atmosphere inside the autoclave with hydrogen, pretreatment was carried out under hydrogen for 5 hours, and then the pressure was removed. The pretreatment conditions were 7.0 MPaG (gauge pressure), 160°C, and a peripheral speed of the impeller at 113 m / min. Subsequently, dehydration was performed under nitrogen for 1 hour. The dehydration conditions were 0.4 MPaG (gauge pressure), 150°C, impeller peripheral speed of 113 m / min, and nitrogen flow rate of 3 NL / min.

[0090] (Step 2) Hydrogenation process After cooling, 14.26 g of the raw material carboxylic acid, "Lunaq L-98" (manufactured by Kao Corporation), was packed into the autoclave. After replacing the atmosphere inside the autoclave with hydrogen, the hydrogenation reaction was carried out in a batch manner for 1.5 hours to obtain lauryl alcohol. The reaction conditions were 7.0 MPaG (gauge pressure), 210°C, a stirring blade peripheral speed of 113 m / min, and a hydrogen flow rate of 1.5 NL / min. The reaction was carried out for 1.5 hours, with the point at which heating and pressurization were completed being considered reaction time 0. Samples were taken as appropriate during the reaction, and the composition of the reaction solution was analyzed. The rate of decrease in acid value and the amount of by-products produced in the reaction time interval from 0.08 hours to 0.25 hours were calculated using the method described above. It was confirmed that the starting carboxylic acid was consumed at 0.50 hours of reaction time. Furthermore, in Examples 2 to 6 and Comparative Example 1, the reaction solution was sampled during a reaction time interval in which the concentration of the starting carboxylic acid present in the reaction solution was approximately the same as that in Example 1. The rate of decrease in acid value and the amount of by-products produced during that reaction time interval were calculated using the method described above.

[0091] Example 2 Lauryl alcohol was obtained in the same manner as in Example 1, except that in (i) preparation of the catalyst precursor, catalyst precursor 1 was changed to catalyst precursor 2, and in (iii) oxidation stabilization treatment of catalyst (A), catalyst 1 obtained was changed to catalyst 2 as shown in Table 1, and the rate of decrease in acid value and the amount of by-products produced in the interval of 0.13 hours to 0.27 hours were calculated using the method described above.

[0092] Example 3 Lauryl alcohol was obtained in the same manner as in Example 1, except that (i) in the preparation of the catalyst precursor, catalyst precursor 1 was changed to catalyst precursor 3, (iii) in the oxidation stabilization treatment of catalyst (A), catalyst 1 obtained was changed to catalyst 3 as shown in Table 1, and the rate of decrease in acid value and the amount of by-products produced in the interval of 0.17 hours to 0.33 hours were calculated using the method described above.

[0093] Example 4 Lauryl alcohol was obtained in the same manner as in Example 1, except that in (i) preparation of the catalyst precursor, catalyst precursor 1 was changed to catalyst precursor 4, and in (iii) oxidation stabilization treatment of catalyst (A), catalyst 1 obtained was changed to catalyst 4 as shown in Table 1, and the rate of decrease in acid value and the amount of by-products produced in the interval of 0.17 hours to 0.33 hours were calculated using the method described above.

[0094] Example 5 Lauryl alcohol was obtained in the same manner as in Example 1, except that in (i) preparation of the catalyst precursor, catalyst precursor 1 was changed to catalyst precursor 5, and in (iii) oxidation stabilization treatment of catalyst (A), catalyst 1 obtained was changed to catalyst 5 as shown in Table 1, and the rate of decrease in acid value and the amount of by-products produced in the interval of 0.17 hours to 0.33 hours were calculated using the method described above.

[0095] Example 6 Lauryl alcohol was obtained in the same manner as in Example 1, except that (i) in the preparation of the catalyst precursor was changed from catalyst precursor 1 to catalyst precursor 6, and (iii) in the oxidation stabilization treatment of catalyst (A) was changed from catalyst 1 to catalyst 6 as shown in Table 1.

[0096] Comparative Example 1 Lauryl alcohol was obtained in the same manner as in Example 1, except that (i) in the preparation of the catalyst precursor, catalyst precursor 1 was changed to catalyst precursor 7; (ii) in the reduction treatment of the catalyst precursor, the reduction treatment temperature was changed from 450°C to 500°C; and (iii) in the oxidation stabilization treatment of catalyst (A), catalyst 1 obtained was changed to catalyst 7 as shown in Table 1; and the rate of decrease in acid value and the amount of by-products produced in the interval of 0.25 hours to 0.42 hours were calculated using the method described above.

[0097] [Table 1]

[0098] The results in Table 1 confirm that Examples 1-6 can suppress the formation of by-products while improving reactivity compared to Comparative Example 1. [Industrial applicability]

[0099] The present invention provides a method for producing alcohol that can suppress the formation of by-products while improving reactivity. < / a1> < / a1> < / a1> < / a13> < / a1> < / a13> < / a1> < / a13> < / a1> < / a13> < / a13> < / a13> < / a13> < / a1> < / a1> < / a1> < / a1> < / a1> < / a1> < / a1> < / a1> < / a1>

Claims

1. In the presence of a catalyst (A) containing Co, Fe, and Zr, A method for producing alcohol, comprising a hydrogenation step in which a raw material carboxylic acid is reacted with hydrogen gas to obtain an alcohol.

2. The method for producing alcohol according to claim 1, wherein the Fe content in the catalyst (A) is 0.1 moles or more and 30 moles or less per 100 moles of Co.

3. The method for producing an alcohol according to claim 1 or 2, wherein the raw material carboxylic acid is an aliphatic carboxylic acid having 8 to 24 carbon atoms.

4. The method for producing alcohol according to claim 1 or 2, wherein the reaction temperature of the hydrogenation step is 150°C or higher and 300°C or lower.

5. The method for producing alcohol according to claim 1 or 2, wherein in the hydrogenation step, the gauge pressure of the hydrogen gas is 1.0 MPaG or more and 10 MPaG or less.

6. A catalyst (A) containing Co, Fe, and Zr, used in a method for producing alcohols using carboxylic acids as raw materials, A catalyst (A) wherein the Fe content is 0.1 moles or more and 30 moles or less per 100 moles of Co.

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