Alcohol production method

Abstract

The present invention relates to a method for producing alcohol from synthesis gas, which improves alcohol selectivity and enables alcohol to be obtained more selectively. A method for producing an alcohol, comprising the following steps 1 and 2: Step 1: A catalyst production step in which a cobalt-containing compound (a) and a lanthanoid-containing compound (b), both soluble in the non-aqueous solvent, are reacted with a divalent or higher carboxylic acid compound (c) in a non-aqueous solvent to obtain a catalyst from the reaction product. Step 2: An alcohol production step in which synthesis gas is reacted in the presence of the catalyst obtained in Step 1 to obtain alcohol.

Description

[Technical Field]

[0001] The present invention relates to a method for producing an alcohol, a method for producing a catalyst, and its use for producing an alcohol. [Background technology]

[0002] Syngas, a mixture of carbon monoxide and hydrogen, is one of the basic raw materials in C1 chemistry and is produced from coal, natural gas, heavy oil, petroleum flue gas, oil shale, biomass, etc. using steam. The composition of the synthesis gas obtained in this way is adjusted depending on the intended use, and it is used in technologies to produce organic compounds from synthesis gas, such as the Fischer-Tropsch reaction (FT reaction). The inventors focused on the technology to produce alcohol from synthesis gas as an application of this technology.

[0003] One such technique is known to produce alcohol by reacting CO and synthesis gas containing H2 in the presence of a cobalt-containing catalyst.

[0004] Patent Document 1 discloses a catalyst for producing alcohol, which comprises an active component, an auxiliary, and a carrier, in which the active component is cobalt, the auxiliary element is one or more selected from rare earth elements, alkaline earth metals, Ti, Mn, Zr, Cu, Al, and B, and the carrier is a silicon-modified petroleum coke-based activator, and also discloses a method for producing alcohol from synthesis gas using this catalyst. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Chinese Patent Publication No. 111375417 Summary of the Invention [Problem to be solved by the invention]

[0006] In recent years, efforts to achieve carbon neutrality have been progressing in various countries, and efforts to develop alternative fuels to reduce carbon dioxide emissions from conventional fossil fuels have been attracting attention. As part of these efforts, there is a method for producing alcohol using synthesis gas containing CO and H2 as a feedstock. As a method for producing alcohol using synthesis gas as a feedstock, alcohol can be produced by a catalytic reaction using the catalysts mentioned above. However, in such catalytic reactions, the proportion of alcohol produced in the reaction products (alcohol selectivity) is insufficient. Even in the invention described in Patent Document 1, the alcohol selectivity in alcohol production using the catalyst remained low.

[0007] The present invention relates to a method for producing alcohol from a synthesis gas containing CO and H2, which improves alcohol selectivity and enables alcohol to be obtained more selectively. [Means for solving the problem]

[0008] The present inventors have found that a catalyst obtained from the reaction product obtained by using a cobalt-containing compound and a lanthanoid-containing compound, both of which are soluble in a non-aqueous solvent, as raw material compounds and reacting them with a precipitant containing a divalent or higher carboxylic acid compound in a non-aqueous solvent can improve alcohol selectivity when producing alcohol from synthesis gas.

[0009] That is, the present invention relates to the following [1] to [3]. [1] A method for producing an alcohol, comprising the following steps 1 and 2: Step 1: A catalyst production step in which a cobalt-containing compound (a) and a lanthanoid-containing compound (b), both soluble in the non-aqueous solvent, are reacted with a divalent or higher carboxylic acid compound (c) in a non-aqueous solvent to obtain a catalyst from the reaction product. Step 2: An alcohol production step in which synthesis gas is reacted in the presence of the catalyst obtained in Step 1 to obtain alcohol. [2] A method for producing a catalyst, comprising reacting a cobalt-containing compound (a) and a lanthanoid-containing compound (b), both of which are soluble in a non-aqueous solvent, with a divalent or higher carboxylic acid compound (c) in a non-aqueous solvent, and obtaining a catalyst from the reaction product. [3] A method for producing alcohol by reacting a cobalt-containing compound (a) and a lanthanoid-containing compound (b), both soluble in the non-aqueous solvent, with a divalent or higher carboxylic acid compound (c) in a non-aqueous solvent, and using a catalyst obtained from the reaction product to react carbon monoxide and hydrogen in a synthesis gas. [Effects of the Invention]

[0010] According to the present invention, there are provided a method for producing alcohol from a synthesis gas, which can improve alcohol selectivity and enable more selective production of alcohol, a method for producing a catalyst used in the alcohol production method, and use of the catalyst for producing alcohol. DETAILED DESCRIPTION OF THE INVENTION

[0011] The method for producing an alcohol of the present invention has the steps described below. [Alcohol production method] The method for producing an alcohol according to the present embodiment includes the following steps 1 and 2. Step 1: A catalyst production step in which a cobalt-containing compound (a) and a lanthanoid-containing compound (b), both soluble in the non-aqueous solvent, are reacted with a divalent or higher carboxylic acid compound (c) in a non-aqueous solvent to obtain a catalyst from the reaction product. Step 2: Reacting synthesis gas in the presence of the catalyst obtained in step 1 to obtain alcohol; Alcohol production process

[0012] According to the present invention, there is provided a method for producing alcohol from a synthesis gas, which can improve the alcohol selectivity and enable more selective production of alcohol.

[0013] In the present invention, "producing alcohol from synthesis gas" means producing alcohol by reacting synthesis gas containing CO (carbon monoxide) and H (hydrogen). Also, in the present invention, "producing alcohol by reacting synthesis gas" means producing alcohol by reacting CO and H in synthesis gas.

[0014] In the present invention, "soluble in a non-aqueous solvent" means that each component dissolves in the non-aqueous solvent described below at the temperature during preparation of the raw material solution, and from the viewpoint of catalyst production efficiency, the solubility is preferably 10 g / 100 g (non-aqueous solvent, 25°C) or more, more preferably 20 g / 100 g (non-aqueous solvent, 25°C) or more.

[0015] The method for producing alcohol according to this embodiment will be described in detail below. <Process 1> Catalyst manufacturing process Step 1 is a catalyst production step in which a cobalt-containing compound (a) and a lanthanoid-containing compound (b), both soluble in a non-aqueous solvent, are reacted with a divalent or higher carboxylic acid compound (c) in a non-aqueous solvent to obtain a catalyst from the reaction product. More specifically, Step 1 is a catalyst production step in which the cobalt-containing compound (a) and the lanthanoid-containing compound (b), both soluble in the non-aqueous solvent, are coprecipitated in the non-aqueous solvent with a precipitating agent containing the divalent or higher carboxylic acid compound (c), and then a catalyst is obtained from the coprecipitated reaction product. In this catalyst production step, the catalyst can be obtained by the catalyst production method described below.

[0016] [Non-aqueous solvent] The non-aqueous solvent used here is a solvent other than water that can dissolve the cobalt-containing compound (a), the lanthanoid-containing compound (b), and the precipitant containing the divalent or higher carboxylic acid compound (c). On the other hand, this non-aqueous solvent does not dissolve but precipitates the reaction product obtained by reacting the precipitant containing the divalent or higher carboxylic acid compound (c) with the cobalt-containing compound (a) and the lanthanoid-containing compound (b).

[0017] The nonaqueous solvent is preferably a solvent that can efficiently proceed with the reaction and obtain a reaction product of uniform composition by coprecipitation. In order to have good solubility for the raw material compounds and to insolubilize the reaction product, the nonaqueous solvent preferably has a relative dielectric constant at 20°C of 3.0 or more, more preferably 10.0 or more, even more preferably 15.0 or more, and preferably 40.0 or less, more preferably 35.0 or less, even more preferably 30.0 or less, and also preferably 3.0 or more and 40.0 or less, more preferably 10.0 or more and 35.0 or less, even more preferably 15.0 or more and 30.0 or less.

[0018] Examples of the non-aqueous solvent include alcohols, ethers, and ketones, and more specifically, examples thereof include alcohols such as ethanol (dielectric constant: 24.6, 20°C), isopropanol (dielectric constant: 18.3, 20°C), 1-propanol (dielectric constant: 20.2, 20°C), and 1-butanol (dielectric constant: 17.3, 20°C), ethers such as diethyl ether (dielectric constant: 4.3, 20°C) and tetrahydrofuran (dielectric constant: 7.6, 20°C), and ketones such as acetone (dielectric constant: 21.5, 20°C). A mixed solvent containing a plurality of solvents may be used as long as it has the above properties. From the above viewpoints, the non-aqueous solvent preferably contains one or more solvents selected from the group consisting of alcohols, ethers, and ketones, more preferably one or more solvents selected from the group consisting of ethanol, isopropanol, 1-propanol, 1-butanol, diethyl ether, tetrahydrofuran, and acetone, even more preferably one or more solvents selected from the group consisting of ethanol and isopropanol, and even more preferably ethanol.

[0019] The non-aqueous solvent may contain water to the extent that it does not affect the reaction. The water content in the non-aqueous solvent may be, for example, less than 1 mass %, less than 0.8 mass %, or less than 0.6 mass %.

[0020] [Cobalt-containing compound (a)] The cobalt-containing compound (a) is a compound that contains cobalt, which serves as a catalytically active material, and dissolves in a non-aqueous solvent. Furthermore, the cobalt-containing compound (a) is a compound that can be coprecipitated with the lanthanoid-containing compound (b) described below by reacting with a precipitating agent containing a divalent or higher carboxylic acid compound (c) in the non-aqueous solvent. Examples of this cobalt-containing compound (a) include cobalt salts, and from the viewpoint of improving catalytic performance, the cobalt-containing compound (a) preferably contains one or more compounds selected from the group consisting of cobalt sulfate, cobalt chloride, cobalt bromide, cobalt iodide, cobalt acetate, and cobalt nitrate, more preferably one or more compounds selected from the group consisting of cobalt acetate and cobalt nitrate, and even more preferably cobalt nitrate.

[0021] [Lanthanoid-containing compounds (b)] The lanthanoid-containing compound (b) is a compound that contains a lanthanoid element and dissolves in a non-aqueous solvent, and can be coprecipitated with the cobalt-containing compound (a) in the non-aqueous solvent by reaction with a precipitating agent containing a divalent or higher carboxylic acid compound (c). The lanthanoid element contained in this lanthanoid element-containing compound (b) is not particularly limited, and is at least one selected from the group consisting of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium, and from the viewpoint of improving catalytic performance, is preferably at least one selected from the group consisting of lanthanum and cerium.

[0022] The lanthanoid element-containing compound (b) is, for example, a salt of a lanthanoid element, and preferably contains at least one selected from the group consisting of sulfates, acetates, nitrates, chlorides, bromides, and iodides. From the viewpoint of improving catalytic performance, this lanthanoid element-containing compound (b) preferably contains at least one selected from the group consisting of lanthanum acetate, lanthanum nitrate, lanthanum sulfate, lanthanum chloride, lanthanum bromide, lanthanum iodide, cerium acetate, cerium nitrate, cerium sulfate, cerium chloride, cerium bromide, and cerium iodide, more preferably at least one selected from the group consisting of lanthanum acetate, lanthanum nitrate, cerium acetate, and cerium nitrate, and even more preferably at least one selected from the group consisting of lanthanum nitrate and cerium nitrate.

[0023] [Precipitant containing divalent or higher carboxylic acid compound (c)] The precipitant contains a divalent or higher carboxylic acid compound (c), i.e., a compound having two or more carboxy groups in one molecule. This precipitant containing a divalent or higher carboxylic acid compound (c) (hereinafter sometimes referred to as "precipitant") is soluble in a non-aqueous solvent, and in the non-aqueous solvent, the carboxylic acid compound reacts with a cobalt-containing compound (a) and a lanthanoid-containing compound (b), resulting in coprecipitating the resulting reaction product (a cobalt-lanthanoid composite compound). The precipitant may contain a divalent or higher carboxylic acid compound. From the viewpoint of improving catalytic performance, the divalent or higher carboxylic acid compound preferably contains a carboxylic acid compound having 2 to 6 carbon atoms, more preferably one or more selected from the group consisting of oxalic acid, malonic acid, succinic acid, malic acid, and citric acid, even more preferably one or more selected from the group consisting of oxalic acid, malic acid, and citric acid, still more preferably one or more selected from the group consisting of oxalic acid and citric acid, and still more preferably oxalic acid. When the precipitating agent contains a divalent or higher carboxylic acid compound, the reactivity with the cobalt-containing compound (a) and the lanthanoid-containing compound (b) becomes good, and a precipitate can be efficiently produced. As a precipitant, other than the divalent or higher carboxylic acid compounds may be added to the extent that the formation of the desired cobalt-lanthanoid composite compound is not inhibited. Examples of such precipitants include sodium carbonate, sodium bicarbonate, and ammonium carbonate.

[0024] [Catalyst manufacturing method] The method for obtaining the catalyst in step 1 (catalyst production step) is a method for obtaining the catalyst from a reactant (cobalt-lanthanoid composite compound) coprecipitated by a predetermined coprecipitation method using the raw material compounds (a cobalt-containing compound and a lanthanoid-containing compound soluble in a non-aqueous solvent) as described above. For example, the coprecipitated reactant is separated and dried, and the resulting dried product is further treated by a conventionally known treatment method for reduction and immobilization to obtain a catalyst. This catalyst production method is preferably a catalyst production method comprising the following steps 1-1 to 1-5. Step 1-1: A step of coprecipitating, in the non-aqueous solvent, a cobalt-containing compound (a) and a lanthanoid-containing compound (b), both of which are soluble in the non-aqueous solvent, with a precipitating agent containing a divalent or higher carboxylic acid compound (c). Step 1-2: A step of separating the reactants coprecipitated in step 1-1 from the mixed solution after the reaction. Step 1-3: A step of drying the precipitate obtained by separation in Step 1-2 Step 1-4: A step of reducing the dried product obtained by drying in Step 1-3 Step 1-5: A step of immobilizing the product reduced in step 1-4 to obtain a catalyst

[0025] Specifically, the cobalt-lanthanoid composite catalyst can be obtained by successively carrying out steps 1-1 to 1-5 described below. <Process 1-1> First, a non-aqueous solvent, a cobalt-containing compound (a) soluble in the non-aqueous solvent, and a lanthanoid-containing compound (b) soluble in the non-aqueous solvent are prepared. Next, the prepared cobalt-containing compound (a) and the lanthanoid-containing compound (b) are uniformly dissolved in the non-aqueous solvent to form a raw material solution. In addition, a precipitating agent containing a divalent or higher carboxylic acid compound (c) is prepared. The prepared precipitating agent may be used as is, or may be dissolved in the non-aqueous solvent and used as a precipitating agent solution.

[0026] Next, the raw material solution is mixed with a precipitant containing a divalent or higher carboxylic acid compound (c), and the cobalt-containing compound (a) and the lanthanoid element-containing compound (b) are reacted with the precipitant (c), resulting in the cobalt-lanthanoid composite compound, which is the reaction product, being coprecipitated (deposited). In this case, when the precipitant is used as it is, the raw material solution and the precipitant are preferably mixed by adding the precipitant to the raw material solution. In addition, when a precipitant solution is used, the precipitant solution may be added to the raw material solution, or the raw material solution may be added to the precipitant solution. However, from the viewpoint of improving catalyst performance, it is preferable to add the precipitant solution to the raw material solution. That is, when a precipitant solution is used, the step 1 preferably includes the following steps 1a, 1b, and 1c, and more preferably includes the following steps 1a, 1b, and 1c'. Step 1a: A step of uniformly dissolving the cobalt-containing compound (a) and the lanthanoid-containing compound (b) in the non-aqueous solvent to obtain a raw material solution. Step 1b: dissolving the precipitant in the non-aqueous solvent to obtain a precipitant solution Step 1c: A step of mixing the raw material solution obtained in step 1a with the precipitant solution obtained in step 1b to co-precipitate the cobalt-containing compound (a) and the lanthanoid-containing compound (b). Step 1c': A step of adding the precipitant solution obtained in step 1b to the raw material solution obtained in step 1a, and coprecipitating the cobalt-containing compound (a) and the lanthanoid-containing compound (b).

[0027] The state of network formation in the cobalt-lanthanoid complex compound obtained is thought to differ depending on the combination of the non-aqueous solvent, cobalt-containing compound (a), lanthanoid-containing compound (b), and precipitant. Although the details are unclear, the state of the network formed here is thought to affect the alcohol selectivity in Step 2, which will be described later.

[0028] <Process 1-2> Next, the reactant (cobalt-lanthanoid composite compound) coprecipitated (precipitated) in step 1-1 is separated from the post-reaction mixed solution. This separation can be performed by a conventional separation procedure in the field of catalyst production, and preferably involves one or more procedures selected from the group consisting of filtration, evaporation to dryness, and centrifugation. Examples of filtration include filter filtration and filtration aid. This separation procedure preferably involves one or more procedures selected from the group consisting of filtration and evaporation to dryness, more preferably one or more procedures selected from the group consisting of filter filtration and evaporation to dryness.

[0029] <Process 1-3> Next, the precipitate obtained by separation in step 1-2 is dried by a drying treatment commonly used in the field of catalyst production in order to remove the non-aqueous solvent. The drying treatment includes one or more selected from the group consisting of air drying, hot air drying, heat drying, and reduced-pressure drying, preferably one or more selected from the group consisting of heat drying and reduced-pressure drying, and more preferably heat drying using a heater.

[0030] <Step 1-4> Furthermore, the dried product obtained by drying in step 1-3 is reduced to obtain a cobalt-lanthanide composite catalyst. This reduction treatment can be carried out by a conventional reduction treatment in the field of catalyst production. A hydrogen-containing gas may be used for the reduction treatment. The hydrogen-containing gas is preferably one or more hydrogen-containing gases selected from the group consisting of a mixed gas of carbon monoxide and hydrogen and a hydrogen-containing inert gas, more preferably a hydrogen-containing inert gas. Here, by carrying out the reduction treatment, cobalt is reduced to metal. The temperature of the reduction treatment (for example, the temperature of the mixed gas of carbon monoxide and hydrogen or the hydrogen-containing inert gas) is preferably 150°C or higher, more preferably 200°C or higher, even more preferably 250°C or higher, and even more preferably 300°C or higher, from the viewpoint of improving catalytic activity, and from the same viewpoint, is preferably 800°C or lower, more preferably 700°C or lower, even more preferably 600°C or lower, and even more preferably 500°C or lower. Also, from the same viewpoint, the temperature is preferably 150°C or higher and 800°C or lower, more preferably 200°C or higher and 700°C or lower, even more preferably 250°C or higher and 600°C or lower, and even more preferably 300°C or higher and 500°C or lower. From the viewpoint of improving catalytic activity, the reduction time of the reduction treatment is preferably more than 0 hours, more preferably 2 hours or more, even more preferably 4 hours or more, still more preferably 6 hours or more, still more preferably 8 hours or more, and from the same viewpoint, preferably 24 hours or less, more preferably 18 hours or less, even more preferably 15 hours or less, and still more preferably 12 hours or less. Also, from the same viewpoint, it is preferably more than 0 hours and 24 hours or less, more preferably 2 hours or more and 18 hours or less, even more preferably 4 hours or more and 15 hours or less, still more preferably 6 hours or more and 12 hours or less, and still more preferably 8 hours or more and 12 hours or less. When the reduction treatment is carried out using the hydrogen-containing gas, the hydrogen concentration in the hydrogen-containing gas during the reduction treatment is, from the viewpoint of improving catalytic activity, preferably 1 vol. % or more, more preferably 2 vol. % or more, even more preferably 3 vol. % or more, and even more preferably 4 vol. % or more, and from the same viewpoint, preferably 100 vol. % or less, more preferably 60 vol. % or less, even more preferably 20 vol. % or less, and even more preferably 10 vol. % or less.

[0031] 〈Process 1-5〉 The product reduced in step 1-4 is then subjected to immobilization treatment in order to improve catalytic activity. The passivation treatment can be carried out by a conventional passivation treatment in the field of catalyst production. For the passivation treatment, an oxygen-containing gas may be used, and the oxygen-containing gas is preferably an oxygen-containing inert gas. Here, the cobalt is stabilized by the passivation treatment. The temperature of the passivation treatment (for example, the temperature of the oxygen-containing inert gas) is preferably 100°C or lower, more preferably 70°C or lower, even more preferably 50°C or lower, and even more preferably 40°C or lower, from the viewpoint of catalyst stabilization through oxide film formation, and from the same viewpoint, is preferably 0°C or higher, more preferably 10°C or higher, even more preferably 20°C or higher, and even more preferably 25°C or higher. Also, from the same viewpoint, the temperature is preferably 0°C or higher to 100°C or lower, more preferably 10°C or higher to 70°C or lower, even more preferably 20°C or higher to 50°C or lower, and even more preferably 25°C or higher to 40°C. From the viewpoint of catalyst stabilization by oxide film formation, the passivation treatment time is preferably 30 minutes or more, more preferably 1 hour or more, even more preferably 2 hours or more, and even more preferably 3 hours or more, and from the same viewpoint, it is preferably 10 hours or less, more preferably 8 hours or less, even more preferably 6 hours or less, and even more preferably 4 hours or less. Also from the same viewpoint, it is preferably 30 minutes to 10 hours, more preferably 1 hour to 8 hours, even more preferably 2 hours to 6 hours, and even more preferably 3 hours to 4 hours. From the viewpoint of catalyst stabilization through oxide film formation, the oxygen concentration in the oxygen-containing gas during the passivation treatment is preferably 0.1 vol% or more, more preferably 0.5 vol% or more, even more preferably 0.8 vol% or more, and even more preferably 1.0 vol% or more, and from the same viewpoint, it is preferably 10 vol% or less, more preferably 6.0 vol% or less, even more preferably 2.0 vol% or less, and even more preferably 1.5 vol% or less.

[0032] In this case, from the viewpoint of improving catalytic performance, the amounts of the cobalt-containing compound (a) and the lanthanoid-containing compound (b) used in the non-aqueous solvent are such that the amount of the lanthanoid element in the lanthanoid-containing compound (b) relative to 1 mol of cobalt in the cobalt-containing compound (a) is preferably 0.05 mol or more and preferably 1.20 mol or less, more preferably 1.00 mol or less, and also preferably 0.05 mol or more and 1.20 mol or less, more preferably 0.05 mol or more and 1.00 mol or less. The amounts of cobalt and lanthanoid element used in this catalyst production method are maintained at the same amounts in the resulting cobalt-lanthanoid composite catalyst.

[0033] When the lanthanoid element of the lanthanoid element-containing compound (b) is lanthanum, from the viewpoint of improving catalytic performance, the amount of the cobalt-containing compound (a) and the lanthanoid element-containing compound (b) blended in the non-aqueous solvent is preferably 0.05 mol or more, more preferably 0.08 mol or more, even more preferably 0.10 mol or more, and preferably 1.20 mol or less, more preferably 0.80 mol or less, even more preferably 0.45 mol or less, and also preferably 0.05 mol or more to 1.20 mol or less, more preferably 0.08 mol or more to 0.80 mol or less, even more preferably 0.10 mol or more to 0.45 mol or less.

[0034] When the lanthanoid element of the lanthanoid element-containing compound (b) is cerium, the amount of the cobalt-containing compound (a) and the lanthanoid element-containing compound (b) blended in the non-aqueous solvent is, from the viewpoint of improving catalytic performance, preferably 0.05 mol or more and preferably 1.20 mol or less, more preferably 0.98 mol or less, even more preferably 0.75 mol or less, still more preferably 0.50 mol or less, still more preferably 0.35 mol or less, and also preferably 0.05 mol or more to 1.20 mol or less, more preferably 0.05 mol or more to 0.98 mol or less, even more preferably 0.05 mol or more to 0.75 mol or less, still more preferably 0.05 mol or more to 0.50 mol or less, still more preferably 0.05 mol or more to 0.35 mol.

[0035] The amount of the precipitant blended in the non-aqueous solvent is such that the molar ratio (precipitant / (cobalt content+lanthanoid content)) of the total content of the cobalt content in the cobalt-containing compound (a) and the lanthanoid content in the lanthanoid-containing compound (b) is preferably 0.90 or more, more preferably 0.95 or more, and is preferably 1.5 or less, more preferably 1.2 or less, and is preferably 0.90 or more and 1.5 or less, more preferably 0.95 or more and 1.2 or less.

[0036] Furthermore, the temperature of the non-aqueous solvent and / or mixture during co-precipitation in the non-aqueous solvent is preferably 5°C or higher, more preferably 15°C or higher, even more preferably 20°C or higher, from the viewpoint of stability of the reactant (precipitate) and prevention of solvent evaporation, and is preferably 50°C or lower, more preferably 40°C or lower, even more preferably 30°C or lower, and is also preferably 5°C or higher and 50°C or lower, more preferably 15°C or higher and 40°C or lower, even more preferably 20°C or higher and 30°C or lower.

[0037] <Process 2> Alcohol production process In this step 2, alcohol is obtained from a synthesis gas containing carbon monoxide (CO) and hydrogen (H2) in the presence of the catalyst obtained in the step 1. In step 2, alcohol is produced by reacting CO and H-containing synthesis gas (feedstock gas) in the presence of a cobalt-lanthanide composite catalyst. For example, alcohol can be produced by placing a solvent and a cobalt-lanthanide composite catalyst in a reaction vessel and passing synthesis gas through the reaction vessel. Since the catalyst and synthesis gas exist in different phases, it is desirable to promote mass transfer between the phases by, for example, bubbling gas into the liquid. In this embodiment, by using the cobalt-lanthanoid composite catalyst obtained by the above-described method, it is possible to improve the alcohol selectivity in the reaction mixture compared to conventionally known methods.

[0038] The synthesis gas used in step 2 is not particularly limited as long as it is a mixed gas containing CO and H. This synthesis gas can be obtained by a conventionally known method, for example, steam reforming by reaction of hydrocarbons such as natural gas or liquefied petroleum gas, or partial oxidation of fuel or biomass. From the viewpoint of improving productivity, the composition of CO and H in the synthesis gas used here is such that the molar ratio of H to CO (H / CO) is preferably 1.0 or more, more preferably 1.3 or more, even more preferably 1.8 or more, and is preferably 2.5 or less, more preferably 2.4 or less, even more preferably 2.2 or less, and is also preferably 1.0 or more and 2.5 or less, more preferably 1.3 or more and 2.4 or less, even more preferably 1.8 or more and 2.2 or less.

[0039] A gas phase exists in the reaction system when producing alcohol in step 2, and it is preferable to carry out the reaction under a synthesis gas atmosphere in order to maintain the activity of the catalyst. From the viewpoint of improving catalyst performance, the reaction pressure (gauge pressure) of this gas phase is preferably 3.0 MPa or more, more preferably 4.0 MPa or more, even more preferably 5.0 MPa or more, and even more preferably 5.5 MPa or more, and from the viewpoint of reducing the burden on equipment and facilities, it is preferably 50 MPa or less, more preferably 30 MPa or less, even more preferably 10 MPa or less, and even more preferably 7.0 MPa or less, and also preferably 3.0 MPa or more and 50 MPa or less, more preferably 4.0 MPa or more and 40 MPa or less, even more preferably 5.0 MPa or more and 30 MPa or less, and even more preferably 5.5 MPa or more and 7.0 MPa or less.

[0040] The temperature of the solvent in step 2 (reaction temperature) is preferably 100°C or higher, more preferably 150°C or higher, even more preferably 200°C or higher, and even more preferably 230°C or higher, from the viewpoint of improving catalytic activity, and is preferably 300°C or lower, more preferably 270°C or lower, and even more preferably 250°C or lower, from the viewpoint of improving energy efficiency, and is also preferably 100°C or higher and 300°C or lower, more preferably 150°C or higher and 300°C or lower, even more preferably 200°C or higher and 270°C or lower, and even more preferably 230°C or higher and 250°C or lower.

[0041] The reactor in which the reaction of step 2 is carried out is preferably a reactor selected from the group consisting of a slurry bed reactor and a fixed bed reactor, more preferably a slurry bed reactor. In particular, from the viewpoints of catalyst durability (suppression of catalyst pore clogging) and stable production (high reaction heat removal efficiency), it is preferable to use a slurry bed reactor using a slurry bed (liquid-phase reaction). Note that the stable production refers to a state in which consistent quality and production volume can be maintained continuously under certain reaction conditions.

[0042] In the alcohol production method of this embodiment, as described above, the alcohol selectivity can be improved in a method for producing alcohol from a synthesis gas containing CO and H, and alcohol can be obtained more selectively. The alcohol obtained in this case is, for example, a straight-chain alcohol having about 1 to 20 carbon atoms, although it is affected by the reaction conditions, etc. The alcohol obtained in this manner can be used as various alcohols and can also be used as a raw material for various organic compounds. Furthermore, among these, alcohols having two or more carbon atoms can be used for applications such as organic solvents, disinfectants, cleaning agents, and fuels. The catalyst produced by the catalyst production method of the present embodiment is obtained in a step corresponding to step 1 in the alcohol production method, and has the effect of improving alcohol selectivity in a method for producing alcohol from a synthesis gas containing CO and H, and is useful as a catalyst in the alcohol production method.

[0043] [Use for producing alcohol] The use for producing an alcohol of this embodiment involves reacting a cobalt-containing compound (a) and a lanthanoid-containing compound (b), which are soluble in the non-aqueous solvent, with a divalent or higher carboxylic acid compound (c) in a non-aqueous solvent, and using the catalyst obtained from the reaction product to react carbon monoxide and hydrogen in a synthesis gas to produce an alcohol.

[0044] In addition to the above-described embodiments, the present invention discloses the following. <1> A method for producing an alcohol, comprising the following steps 1 and 2: Step 1: A catalyst production step in which a cobalt-containing compound (a) and a lanthanoid-containing compound (b), both soluble in the non-aqueous solvent, are coprecipitated in a non-aqueous solvent with a precipitating agent containing a divalent or higher carboxylic acid compound (c), and a catalyst is obtained from the coprecipitated reaction product. Step 2: An alcohol production step in which synthesis gas is reacted in the presence of the catalyst obtained in Step 1 to obtain alcohol. <2> The non-aqueous solvent has a relative dielectric constant at 20°C of 3.0 or more and 40.0 or less, preferably 10.0 or more and 35.0 or less, and more preferably 15.0 or more and 30.0 or less. <1> A method for producing the alcohol described in <3> the non-aqueous solvent is at least one selected from the group consisting of alcohols, ethers, and ketones, preferably at least one selected from the group consisting of ethanol, isopropanol, 1-propanol, 1-butanol, diethyl ether, tetrahydrofuran, and acetone, and contains at least one selected from the group consisting of ethanol and isopropanol, more preferably at least one selected from the group consisting of ethanol and isopropanol, and even more preferably ethanol; <1> or <2> A method for producing the alcohol described in <4> The cobalt-containing compound (a) is a cobalt salt, preferably at least one selected from the group consisting of cobalt sulfate, cobalt chloride, cobalt bromide, cobalt iodide, cobalt acetate, and cobalt nitrate, more preferably at least one selected from the group consisting of cobalt acetate and cobalt nitrate, and even more preferably cobalt nitrate. <1> ~ <3> 10. The method for producing an alcohol according to claim 9, wherein <5> the lanthanoid element of the lanthanoid element-containing compound (b) is at least one selected from the group consisting of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium, preferably at least one selected from the group consisting of lanthanum and cerium, more preferably at least one selected from the group consisting of lanthanum and cerium; <1> ~ <4> 10. The method for producing an alcohol according to claim 9, wherein <6> The lanthanoid element-containing compound (b) is a salt of a lanthanoid element, and is preferably at least one selected from the group consisting of sulfates, acetates, nitrates, chlorides, bromides, and iodides, more preferably at least one selected from the group consisting of lanthanum acetate, lanthanum nitrate, lanthanum sulfate, lanthanum chloride, lanthanum bromide, lanthanum iodide, cerium acetate, cerium nitrate, cerium sulfate, cerium chloride, cerium bromide, and cerium iodide, even more preferably at least one selected from the group consisting of lanthanum acetate, lanthanum nitrate, cerium acetate, and cerium nitrate, and still more preferably at least one selected from the group consisting of lanthanum nitrate and cerium nitrate. <1> ~ <5> 10. The method for producing an alcohol according to claim 9, wherein <7> In the step 1, the amount of the lanthanoid element in the lanthanoid element-containing compound (b) relative to 1 mol of cobalt in the cobalt-containing compound (a) is preferably 0.05 mol or more, and preferably 1.20 mol or less, more preferably 1.00 mol or less, and also preferably 0.05 mol or more and 1.20 mol or less, more preferably 0.05 mol or more and 1.00 mol or less. <1> ~ <6> 10. The method for producing an alcohol according to claim 9, wherein <8> the precipitant is a carboxylic acid compound having 2 to 6 carbon atoms, preferably one or more selected from the group consisting of oxalic acid, malonic acid, succinic acid, malic acid, and citric acid, more preferably one or more selected from the group consisting of oxalic acid, malic acid, and citric acid, even more preferably one or more selected from the group consisting of oxalic acid and citric acid, still more preferably one or more selected from the group consisting of oxalic acid and citric acid, still more preferably oxalic acid; <1> ~ <7> 10. The method for producing an alcohol according to claim 9, wherein <9> the cobalt-containing compound (a) is one or more cobalt salts selected from the group consisting of cobalt acetate and cobalt nitrate; the lanthanoid element of the lanthanoid-containing compound (b) is at least one selected from the group consisting of lanthanum and cerium; the precipitating agent is at least one selected from the group consisting of oxalic acid and citric acid, The non-aqueous solvent is at least one selected from the group consisting of ethanol and isopropanol. <1> ~ <8> 10. The method for producing an alcohol according to claim 9, wherein <10> the cobalt-containing compound (a) is cobalt nitrate; the lanthanoid element of the lanthanoid-containing compound (b) is lanthanum; the precipitating agent is oxalic acid; The non-aqueous solvent is ethanol. <1> ~ <9> 10. The method for producing an alcohol according to claim 9, wherein <11> the cobalt-containing compound (a) is a cobalt salt selected from the group consisting of cobalt acetate and cobalt nitrate; the lanthanoid-containing compound (b) is at least one selected from the group consisting of lanthanum nitrate and cerium nitrate; the precipitating agent is at least one selected from the group consisting of oxalic acid and citric acid, The non-aqueous solvent is at least one selected from the group consisting of ethanol and isopropanol. <1> ~ <9> 10. The method for producing an alcohol according to claim 9, wherein <12> the cobalt-containing compound (a) is cobalt nitrate; the lanthanoid-containing compound (b) is lanthanum nitrate; the precipitating agent is oxalic acid; The non-aqueous solvent is ethanol. <1> ~ <11> 10. The method for producing an alcohol according to claim 9, wherein <13> The molar ratio of hydrogen to carbon monoxide (H2 / CO) of the synthesis gas is preferably 1.0 or more, more preferably 1.3 or more, even more preferably 1.8 or more, and is preferably 2.5 or less, more preferably 2.4 or less, even more preferably 2.2 or less, and is also preferably 1.0 or more and 2.5 or less, more preferably 1.3 or more and 2.4 or less, even more preferably 1.8 or more and 2.2 or less. <1> ~ <12> 10. The method for producing an alcohol according to claim 9, wherein <14> The step 1 includes the following steps 1a, 1b, and 1c: <1> ~ <13> 10. The method for producing an alcohol according to claim 9, wherein Step 1a: A step of uniformly dissolving the cobalt-containing compound (a) and the lanthanoid-containing compound (b) in the non-aqueous solvent to obtain a raw material solution. Step 1b: dissolving the precipitant in the non-aqueous solvent to obtain a precipitant solution Step 1c: A step of mixing the raw material solution obtained in Step 1a with the precipitant solution obtained in Step 1b to co-precipitate the cobalt-containing compound (a) and the lanthanoid-containing compound (b). <15> The step 1c is the following step 1c': <14> Step 1c': adding the precipitant solution obtained in step 1b to the raw material solution obtained in step 1a, thereby coprecipitating the cobalt-containing compound (a) and the lanthanoid-containing compound (b). <16> In the step 1, the method further comprises a step of separating the coprecipitated reaction product from the mixed solution after the reaction and drying the reaction product. <1> ~ <15> 10. The method for producing an alcohol according to claim 9, wherein <17> In the step 1, the method includes a step of separating the coprecipitated reaction product from the mixed solution after the reaction and drying the reaction product, and the drying is performed by one or more methods selected from the group consisting of air drying, hot air drying, heat drying, and reduced-pressure drying, preferably by one or more methods selected from the group consisting of heat drying and reduced-pressure drying, and more preferably by heat drying using a heater. <1> ~ <16> 10. The method for producing an alcohol according to claim 9, wherein <18> The method includes steps of separating the reactant coprecipitated in step 1 from the mixed solution after the reaction, drying the reactant, and subjecting the dried product to a reduction treatment and a passivation treatment. <1> ~ <17> 10. The method for producing an alcohol according to claim 9, wherein <19> In the step 1, the catalyst is obtained by reducing the coprecipitated reactant, and the reduction is carried out with a hydrogen-containing gas, preferably one or more hydrogen-containing gases selected from the group consisting of a mixed gas of carbon monoxide and hydrogen and a hydrogen-containing inert gas. <1> ~ <18> 10. The method for producing an alcohol according to claim 9, wherein <20> In step 1, the catalyst is obtained by reducing the coprecipitated reactant, and the temperature of the reduction treatment is preferably 150°C or higher, more preferably 200°C or higher, even more preferably 250°C or higher, still more preferably 300°C or higher, and preferably 800°C or lower, more preferably 700°C or lower, even more preferably 600°C or lower, and still more preferably 500°C or lower; and from the same viewpoint, preferably 150°C or higher and 800°C or lower, more preferably 200°C or higher and 700°C or lower, even more preferably 250°C or higher and 600°C or lower, and still more preferably 300°C or higher and 500°C or lower. <1> ~ <19> 10. The method for producing an alcohol according to claim 9, wherein <21> In step 1, the catalyst is obtained by subjecting the coprecipitated reactant to a reduction treatment, and the time for the reduction treatment is preferably more than 0 hours, more preferably 2 hours or more, even more preferably 4 hours or more, still more preferably 6 hours or more, still more preferably 8 hours or more, and preferably 24 hours or less, more preferably 18 hours or less, even more preferably 15 hours or less, and still more preferably 12 hours or less; and from the same viewpoint, it is preferably more than 0 hours and 24 hours or less, more preferably 2 hours or more and 18 hours or less, even more preferably 4 hours or more and 15 hours or less, still more preferably 6 hours or more and 12 hours or less, and still more preferably 8 hours or more and 12 hours or less. <1> ~ <20> 10. The method for producing an alcohol according to claim 9, wherein <22> In the step 1, the catalyst is obtained by reducing the coprecipitated reactant, and the reduction is preferably carried out with one or more hydrogen-containing gases selected from the group consisting of a mixed gas of carbon monoxide and hydrogen and a hydrogen-containing inert gas, and the hydrogen concentration in the hydrogen-containing gas during the reduction is preferably 1% by volume or more, more preferably 2% by volume or more, even more preferably 3% by volume or more, still more preferably 4% by volume or more, and preferably 100% by volume or less, more preferably 60% by volume or less, even more preferably 20% by volume or less, and still more preferably 10% by volume or less. <1> ~ <21> 10. The method for producing an alcohol according to claim 9, wherein <23> In the step 1, the catalyst is obtained by subjecting the coprecipitated reactant to a reduction treatment and then to a passivation treatment, and the passivation treatment is carried out using an oxygen-containing gas, preferably an oxygen-containing inert gas. <1> ~ <22> 10. The method for producing an alcohol according to claim 9, wherein <24> In step 1, the catalyst is obtained by subjecting the coprecipitated reactant to a reduction treatment and then to a passivation treatment, and the temperature of the passivation treatment is preferably 100°C or lower, more preferably 70°C or lower, even more preferably 50°C or lower, and even more preferably 40°C or lower, and is preferably 0°C or higher, more preferably 10°C or higher, even more preferably 20°C or higher, and even more preferably 25°C or higher, and is also preferably 0°C or higher and 100°C or lower, more preferably 10°C or higher and 70°C or lower, even more preferably 20°C or higher and 50°C or lower, and even more preferably 25°C or higher and 40°C or lower. <1> ~ <23> 10. The method for producing an alcohol according to claim 9, wherein <25> In step 1, the catalyst is obtained by subjecting the coprecipitated reactant to a reduction treatment and then to a passivation treatment, and the time for the passivation treatment is preferably 30 minutes or more, more preferably 1 hour or more, even more preferably 2 hours or more, still more preferably 3 hours or more, and preferably 10 hours or less, more preferably 8 hours or less, even more preferably 6 hours or less, still more preferably 4 hours or less, and also preferably 30 minutes to 10 hours, more preferably 1 hour to 8 hours, even more preferably 2 hours to 6 hours, still more preferably 3 hours to 4 hours. <1> ~ <24> 10. The method for producing an alcohol according to claim 9, wherein <26> In the step 1, the catalyst is obtained by subjecting the coprecipitated reactant to a reduction treatment and then to a passivation treatment, and the passivation treatment is carried out using an oxygen-containing gas, and the oxygen concentration in the oxygen-containing gas during the passivation treatment is preferably 0.1% by volume or more, more preferably 0.5% by volume or more, even more preferably 0.8% by volume or more, still more preferably 1.0% by volume or more, and preferably 10% by volume or less, more preferably 6.0% by volume or less, even more preferably 2.0% by volume or less, and still more preferably 1.5% by volume or less. <1> ~ <25> 10. The method for producing an alcohol according to claim 9, wherein <27> Step 1 is a catalyst production step in which a cobalt-containing compound (a) and a lanthanoid-containing compound (b), both soluble in the non-aqueous solvent, are coprecipitated in a non-aqueous solvent with a precipitating agent containing a divalent or higher carboxylic acid compound (c), and then a catalyst is obtained from the coprecipitated reaction product. <1> ~ <26> 10. The method for producing an alcohol according to claim 9, wherein <28> The reaction in step 2 is carried out in an apparatus selected from the group consisting of a slurry bed reactor and a fixed bed reactor, preferably a slurry bed reactor. <1> ~ <27> 10. The method for producing an alcohol according to claim 9, wherein <29> In the step 2, a gas phase is present in the reaction system when producing an alcohol, and the reaction pressure (gauge pressure) of this gas phase is preferably 3.0 MPa or more, more preferably 4.0 MPa or more, even more preferably 5.0 MPa or more, still more preferably 5.5 MPa or more, and preferably 50 MPa or less, more preferably 30 MPa or less, even more preferably 10 MPa or less, still more preferably 7.0 MPa or less, and also preferably 3.0 MPa or more and 50 MPa or less, more preferably 4.0 MPa or more and 40 MPa or less, still more preferably 5.0 MPa or more and 30 MPa or less, still more preferably 5.5 MPa or more and 7.0 MPa or less. <1> ~ <28> 10. The method for producing an alcohol according to claim 9, wherein <30> The reaction temperature in step 2 is preferably 100°C or higher, more preferably 150°C or higher, even more preferably 200°C or higher, still more preferably 230°C or higher, and preferably 300°C or lower, more preferably 270°C or lower, even more preferably 250°C or lower, and also preferably 100°C or higher and 300°C or lower, more preferably 150°C or higher and 300°C or lower, even more preferably 200°C or higher and 270°C or lower, and still more preferably 230°C or higher and 250°C or lower. <1> ~ <29> 10. The method for producing an alcohol according to claim 9, wherein <31> In the step 2, a gas phase is present in the reaction system when producing alcohol, the reaction pressure (gauge pressure) of the gas phase is 3.0 MPa or more and 50 MPa or less, and the reaction temperature is 100°C or more and 300°C or less. <1> ~ <30> 10. The method for producing an alcohol according to claim 9, wherein <32> In the step 2, a gas phase is present in the reaction system when producing alcohol, the reaction pressure (gauge pressure) of the gas phase is 3.0 MPa or more and 50 MPa or less, and the reaction temperature is 150°C or more and 300°C or less. <1> ~ <31> 10. The method for producing an alcohol according to claim 9, wherein <33> In the step 2, a gas phase is present in the reaction system when producing alcohol, the synthesis gas is reacted in a synthesis gas atmosphere, the reaction pressure (gauge pressure) is 4.0 MPa or more and 40 MPa or less, and the reaction temperature is 200°C or more and 270°C or less. <1> ~ <32> 10. The method for producing an alcohol according to claim 9, wherein <34> In the step 2, a gas phase is present in the reaction system when producing alcohol, the synthesis gas is reacted under a synthesis gas atmosphere, the reaction pressure (gauge pressure) of the gas phase is 5.0 MPa or more and 30 MPa or less, and the reaction temperature is 230°C or more and 250°C or less. <1> ~ <33> 10. The method for producing an alcohol according to claim 9, wherein <35> In the step 2, a gas phase is present in the reaction system when producing alcohol, the synthesis gas is reacted under a synthesis gas atmosphere, the reaction pressure (gauge pressure) of the gas phase is 5.5 MPa or more and 7.0 MPa or less, and the reaction temperature is 230°C or more and 250°C or less. <1> ~ <34> 10. The method for producing an alcohol according to claim 9, wherein <36> A method for producing a catalyst, comprising reacting a cobalt-containing compound (a) and a lanthanoid-containing compound (b), both of which are soluble in a non-aqueous solvent, with a divalent or higher carboxylic acid compound (c) in a non-aqueous solvent, and obtaining a catalyst from the reaction product. <37> A method for producing a catalyst, comprising the following step 1: Step 1: A step of coprecipitating a cobalt-containing compound (a) and a lanthanoid-containing compound (b), both soluble in the non-aqueous solvent, with a precipitating agent containing a divalent or higher carboxylic acid compound (c) in a non-aqueous solvent, and then obtaining a catalyst from the coprecipitated reaction product. <38> The method further comprises a step of separating the coprecipitated reaction product from the mixed solution after the reaction in the step 1. <37> A method for producing the catalyst described in <39> The method further comprises a step of drying the precipitate separated in step 1. <38> A method for producing the catalyst described in <40> The method further comprises a step of reducing the dried product obtained by drying in the step 1. <39> A method for producing the catalyst described in <41> Further, the method includes a step of immobilizing the reduction product obtained by the reduction. <40> A method for producing the catalyst described in <42> A method for producing a catalyst, comprising the following steps 1-1 to 1-5. Step 1-1: A step of coprecipitating, in a non-aqueous solvent, a cobalt-containing compound (a) and a lanthanoid-containing compound (b), both of which are soluble in the non-aqueous solvent, with a precipitant containing a divalent or higher carboxylic acid compound (c). Step 1-2: A step of separating the reactants coprecipitated in step 1-1 from the mixed solution after the reaction. Step 1-3: A step of drying the precipitate obtained by separation in Step 1-2 Step 1-4: A step of reducing the dried product obtained by drying in Step 1-3 Step 1-5: A step of immobilizing the product reduced in step 1-4 to obtain a catalyst <43> <36> ~ <42> 1. A method for producing an alcohol, comprising reacting a synthesis gas in the presence of a catalyst obtained by the method for producing a catalyst according to any one of the above items 1 to 5 to obtain an alcohol. <44> A method for producing an alcohol by reacting a cobalt-containing compound (a) and a lanthanoid-containing compound (b), which are soluble in the non-aqueous solvent, with a divalent or higher carboxylic acid compound (c) in a non-aqueous solvent, and using a catalyst obtained from the reaction product to react carbon monoxide and hydrogen in a synthesis gas. [Example]

[0045] The present invention will be described in detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples. Measurements and evaluations in the examples were carried out by the methods described below. Unless otherwise specified, the samples were prepared at room temperature (25°C) and atmospheric pressure.

[0046] (Example 1: Co-La catalyst a) A stirrer tip (size 4.0 cm) was placed in a 0.5 L container, and 6.74 g (cobalt 23.2 mmol) of cobalt (II) nitrate hexahydrate (Kanto Chemical Co., Ltd.), 0.47 g (lanthanum 1.09 mmol) of lanthanum (II) nitrate hexahydrate (Kanto Chemical Co., Ltd.), and 120 mL of ethanol were added. The mixture was stirred at 600 rpm for 30 minutes to prepare mixed solution 1 (raw solution: La / Co molar ratio 0.05). A 0.5 L container was equipped with a stirrer tip (size 4.0 cm), and 2.18 g (24.2 mmol) of oxalic acid and 230 mL of ethanol were added and stirred at 600 rpm for 30 minutes to prepare a precipitant solution. After stirring, 120 mL of Mixture 1 was added dropwise to the precipitant solution over 30 minutes. After addition, the mixture was stirred at 600 rpm for 30 minutes. After stirring, the precipitate was filtered using a 0.2 μm pore size membrane filter (manufactured by ADVANTEC). The filtered material was dried in an air atmosphere at 120°C for 16 hours. The dried catalyst was placed in a reduction furnace (muffle furnace) for 30 minutes and then cooled to room temperature (25°C). The air in the muffle furnace was replaced with nitrogen, and the muffle furnace was heated from room temperature (25°C) to 400°C over 3 hours while nitrogen containing 4% hydrogen by volume was passed through the muffle furnace at atmospheric pressure at 40 mL per minute. The reduction was then carried out by holding at 400°C for 10 hours. After completion of the reduction, the nitrogen flow rate was changed to 40 mL per minute, and the catalyst was cooled to room temperature (25°C). After that, nitrogen containing 1% oxygen by volume was passed through the muffle furnace at 15 mL per minute for 240 minutes to perform surface passivation treatment, yielding Co-La catalyst a.

[0047] Next, a semi-batch autoclave (C-401, manufactured by Toyo Koatsu Co., Ltd.) with an internal volume of 100 mL was used as the reactor for producing alcohol from synthesis gas. 40 mL of n-hexadecane (manufactured by Kanto Chemical Co., Ltd.) and 0.5 g of a catalyst with an average particle size of 1 μm were placed in the reactor. After the inside of the piping was purged with nitrogen, synthesis gas (H2 / CO (molar ratio) = 2.0, hydrogen content = 65 vol%, carbon monoxide content = 32 vol%, argon content = 3 vol%) was supplied and vented at 10 L / min to raise the gauge pressure to 6.0 MPa. After the pressure was raised, the temperature was raised from room temperature (25 °C) to 240 °C over 1 hour and 30 minutes. The reaction started when the temperature reached 240 °C. The reactor was stirred at 1200 rpm and the reaction was allowed to proceed for 3 hours, yielding a reaction product containing alcohol.

[0048] (Examples 2 to 3a: Co-La catalysts b to c) The same procedure as in Example 1 was carried out except that the compounds and amounts used were as shown in Table 1, to obtain Co-La catalyst b (Example 2) and Co-La catalyst c (Example 3a). Furthermore, the obtained Co-La catalysts bc were subjected to the same procedure as in Example 1 to obtain a reaction product containing alcohol from the synthesis gas. Example 3b A Co-La catalyst c' was obtained in the same manner as in Example 3a, except that the precipitant solution was added dropwise to the raw material solution. Furthermore, the obtained Co-La catalyst c' was subjected to the same procedure as in Example 1 to obtain a reaction product containing alcohol from the synthesis gas.

[0049] (Example 4: Co-La catalyst d) A 1.0 L vessel was charged with a stirrer tip (4.0 cm diameter), and 350 mL of cobalt(II) nitrate hexahydrate (Kanto Chemical), lanthanum(II) nitrate hexahydrate (Kanto Chemical), and ethanol were added. The resulting mixture was stirred at 600 rpm for 30 minutes to prepare a raw material solution. Citric acid (Kanto Chemical) was added to the resulting mixture in the amount shown in Table 1, and the mixture was stirred at 600 rpm for 30 minutes. The stirrer tip was then removed from the vessel, and the solvent was removed using an evaporator (BUCHI Catalog No. U00210), resulting in the recovery of the precipitate. The precipitate was dried in an air atmosphere at 120°C for 16 hours. The dried catalyst was placed in a reduction furnace (muffle furnace) for 30 minutes and cooled to room temperature (25°C). The air in the muffle furnace was replaced with nitrogen, and the muffle furnace was heated from room temperature (25°C) to 400°C over 3 hours while nitrogen containing 4% by volume of hydrogen was passed through the furnace at atmospheric pressure at 40 mL per minute. The furnace was then maintained at 400°C for 10 hours to carry out reduction. After completion of reduction, the nitrogen flow rate was switched to 40 mL per minute, and the catalyst was cooled to room temperature (25°C). Then, nitrogen containing 1% by volume of oxygen was passed through the muffle furnace at 15 mL per minute for 240 minutes to perform surface passivation treatment, yielding Co-La catalyst d (Example 4). Furthermore, the obtained Co-La catalyst d was subjected to the same procedure as in Example 1 to obtain a reaction product containing alcohol from the synthesis gas.

[0050] (Examples 5-6: Co-La catalysts e-f) The same procedure as in Example 1 was carried out except that the compounds and amounts used were as shown in Table 1, to obtain Co-La catalyst e (Example 5) and Co-La catalyst f (Example 6). Furthermore, the obtained Co-La catalysts e to f were subjected to the same procedures as in Example 1 to obtain a reaction product containing alcohol from the synthesis gas.

[0051] (Examples 7 to 10: Co-Ce catalysts g to j) Co-Ce catalyst g (Example 7), Co-Ce catalyst h (Example 8), Co-Ce catalyst i (Example 9), and Co-Ce catalyst j (Example 10) were obtained by the same procedure as in Example 1, except that the compounds and amounts used were as shown in Table 1. In these examples, cerium nitrate was used as the raw material instead of lanthanum nitrate. Furthermore, the obtained Co-Ce catalysts g to j were subjected to the same procedure as in Example 1 to obtain a reaction product containing alcohol from the synthesis gas.

[0052] (Comparative Example 1: Production of Co catalyst) A Co catalyst was obtained in the same manner as in Example 1, except that the compounds and amounts used were as shown in Table 1. Furthermore, the obtained Co catalyst was subjected to the same procedure as in Example 1 to obtain a reaction product containing alcohol from the synthesis gas. (Comparative example 2: Co-La catalyst C1) Co-La catalyst C1 was obtained in the same manner as in Example 3b, except that the compounds and amounts used were as shown in Table 1. In this example, water (relative dielectric constant: 80.0) was used as the solvent during catalyst formation. Furthermore, the obtained Co-La catalyst C1 was subjected to the same procedure as in Example 1 to obtain a reaction product containing alcohol from the synthesis gas.

[0053] The catalyst, synthesis gas, and reaction products obtained as described above were analyzed for composition and components, and the CO conversion and selectivity for each compound were calculated. The results are summarized in Table 1.

[0054] [Method for analyzing gas components during reaction] The gas components during the reaction were introduced every hour through the outlet pipe from the reactor into a gas chromatograph (also called GC) equipped with a thermal conductivity detector (also called TCD) or a flame ionization detector (also called FID), and GC analysis was performed using argon as an internal standard substance.

[0055] The volumetric concentration of carbon monoxide in the gaseous components was calculated from the GC peak area percentages derived from carbon monoxide and argon by the internal standard method using argon as the internal standard. A calibration curve was created by measuring a mixture of standard gases consisting of carbon monoxide, methane, and carbon dioxide, as well as argon, and plotting the peak area ratio of carbon monoxide and argon against the volumetric concentration ratio of carbon monoxide and argon at each mixture ratio.

[0056] The volume concentration of methane in the gaseous components was calculated from the GC peak area percentages of methane and argon by the internal standard method using argon as the internal standard. A calibration curve was created by measuring a mixture of standard gases consisting of carbon monoxide, methane, and carbon dioxide, as well as argon, and plotting the peak area ratios of carbon monoxide and argon against the volume concentration ratio of methane and argon at each mixture ratio.

[0057] The volume concentration of the olefin in the gas component was calculated by the following formula. Volume concentration % of olefins = Volume concentration % of methane × (GC peak area derived from all detected olefins of all carbon numbers / GC peak area derived from detected methane)

[0058] The volume concentration of paraffin in the gas component was calculated using the following formula. Volume concentration % of paraffin = Volume concentration % of methane × (GC peak area derived from paraffins of all detected carbon numbers / GC peak area derived from detected methane)

[0059] <GC measurement conditions> CO and methane Sample introduction volume: 1 mL Gas chromatography: GC-320 (GL Sciences) Detector: TCD (built into gas chromatograph) Column: Active Carbon (GL Sciences, 60-80 mesh, column length 3 m, inner diameter 2 mm) Temperature conditions: 80℃ constant Carrier gas: H2, inlet pressure 200 kPa Sample introduction temperature: 110°C, detector temperature: 80°C Olefins and paraffins Sample volume: 0.8 mL Gas chromatography: GC-14B (Shimadzu Corporation) Detector: FID (built into gas chromatograph) Column: Porapak Q (GL Sciences, packing mesh size 80 / 100, column length 3 m, inner diameter 2 mm) Temperature conditions: 70℃ → 230℃ (heating rate: 2℃ / min) Carrier gas: N2, inlet pressure 200 kPa Sample introduction temperature: 200°C, detector temperature: 230°C

[0060] [Analysis of liquid components of reaction product at the end of reaction] After the reaction was completed, the reactor and ice trap were removed. The products in the ice trap were mixed in the reactor, and deionized water was added to the mixture to separate the organic and aqueous layers. As internal standards, 0.1 g of 1-octanol (Kanto Chemical) and 0.1 g of dodecane (Kanto Chemical) were added to the organic layer, and 0.05 g of tert-butanol (Kanto Chemical) was added to the aqueous layer. After thorough stirring, the resulting solution was analyzed by GC. 0.2 μL of each sample was introduced directly into the GC for GC analysis. The alcohol concentrations in the organic layer were calculated using a conversion formula based on the area percentage of the detected GC peaks derived from each alcohol and the area percentage of the GC peak derived from dodecane. The conversion formula was determined from the peak areas of known concentrations of each alcohol and known concentrations of 1-octanol. The concentrations of olefins and paraffins in the organic layer were calculated using a conversion formula based on the area percentage of the detected GC peaks derived from each olefin and paraffin and the area percentage of the GC peak derived from dodecane. The conversion formula was calculated from the peak areas of known concentrations of each olefin, paraffin, and dodecane. The alcohol concentration in the aqueous layer was calculated using a conversion formula based on the area percentage of the detected GC peaks derived from each alcohol and the area percentage of the GC peak derived from tert-butanol. The conversion formula was calculated from the peak areas of known concentrations of each alcohol and known concentrations of tert-butanol. ·GC measurement conditions Sample introduction volume: 0.2 μL Gas chromatography: GC-2014 (Shimadzu Corporation)

[0061] [Methods for calculating CO conversion, alcohol selectivity, and alcohol selectivity with two or more carbon atoms] CO conversion, alcohol selectivity, and alcohol selectivity for carbon atoms of 2 or more (C 2+ The alcohol selectivity was calculated according to the following formula: In the formula below, C-mol% (carbon mole %) is the ratio of the number of moles of carbon atoms in each product to the number of moles of carbon atoms in all products, and is expressed by the following formula. C-mol% (carbon mole %) = (number of moles of carbon atoms in each product / number of moles of carbon atoms in all products) x 100 The total amount of HC produced represents the total amount of hydrocarbons produced and is calculated using the following formula: Total amount of HC produced (C-mol%) = Total amount of olefin produced (C-mol%) + Total amount of paraffin produced (C-mol%) With respect to the CO conversion rate, alcohol selectivity, and alcohol selectivity for alcohols having two or more carbon atoms, the higher the numerical value, the better the performance of the catalyst in light of the object of the present invention.

[0062] ·Reactant calculation formula CO conversion rate (%) = (1 - (CO concentration (mol%) in the gas components at the reactor outlet / CO concentration (mol%) in the gas supplied to the reactor)) × 100 Alcohol selectivity (%; C-mol ratio) = (total amount of ROH produced (C-mol%) / (total amount of ROH produced (C-mol%) + total amount of HC produced (C-mol%))) × 100 C 2+ Alcohol selectivity (%; C-mol ratio) = (C 2+ Total amount of ROH generated (C-mol%) / (Total amount of ROH generated (C-mol%) + Total amount of HC generated (C-mol%)) × 100 Here, the total amount of ROH produced is calculated by dividing the total amount of alcohol produced by C 2+The total amount of ROH produced means the total amount of alcohols produced that have two or more carbon atoms. Therefore, C 2+ The alcohol selectivity means the selectivity of alcohols having two or more carbon atoms, and differs from the alcohol selectivity in that it does not include methanol.

[0063] [Table 1]

[0064] From the above, it was found that in the alcohol production method of the present embodiment, by setting the production conditions of the obtained catalyst to predetermined conditions, the alcohol selectivity can be improved when alcohol is produced from synthesis gas using the catalyst.

Claims

1. The method includes the following steps 1 and 2: Step 1: A catalyst production step in which a cobalt-containing compound (a) and a lanthanoid-containing compound (b), both soluble in the non-aqueous solvent, are reacted with a divalent or higher carboxylic acid compound (c) in a non-aqueous solvent, and a catalyst is obtained from the reaction product at 500°C or lower. Step 2: An alcohol production step in which synthesis gas is reacted in the presence of the catalyst obtained in Step 1 to obtain alcohol. In the step 1, the amount of the lanthanoid element in the lanthanoid element-containing compound (b) relative to 1 mol of cobalt in the cobalt-containing compound (a) is 0.05 mol or more and 1.20 mol or less; When the lanthanoid element of the lanthanoid element-containing compound (b) is lanthanum, the amounts of the cobalt-containing compound (a) and the lanthanoid element-containing compound (b) blended in the non-aqueous solvent are such that the amount of the lanthanoid element of the lanthanoid element-containing compound (b) relative to 1 mol of cobalt in the cobalt-containing compound (a) is 0.05 mol or more and 0.80 mol or less; When the lanthanoid element of the lanthanoid element-containing compound (b) is cerium, the blending amounts of the cobalt-containing compound (a) and the lanthanoid element-containing compound (b) in the non-aqueous solvent are such that the amount of the lanthanoid element of the lanthanoid element-containing compound (b) relative to 1 mol of cobalt in the cobalt-containing compound (a) is 0.05 mol or more and 0.98 mol or less. Methods for producing alcohol.

2. 2. The method for producing an alcohol according to claim 1, wherein the non-aqueous solvent has a relative dielectric constant at 20°C of 3.0 or more and 40.0 or less.

3. The method for producing an alcohol according to claim 2, wherein the non-aqueous solvent contains at least one solvent selected from the group consisting of ethanol and isopropanol.

4. The method for producing an alcohol according to any one of claims 1 to 3, wherein the lanthanoid element in the lanthanoid-containing compound (b) is at least one selected from the group consisting of lanthanum and cerium.

5. 4. The method for producing an alcohol according to claim 1, wherein, in step 1, when the lanthanoid element in the lanthanoid-element-containing compound (b) is lanthanum, the amount of the lanthanoid element in the lanthanoid-element-containing compound (b) relative to 1 mol of cobalt in the cobalt-containing compound (a) is 0.05 mol or more and 0.45 mol or less.

6. The method for producing an alcohol according to any one of claims 1 to 3, wherein the (c) contains one or more acids selected from the group consisting of oxalic acid and citric acid.

7. 4. The method for producing an alcohol according to claim 1, wherein the step 1 is a catalyst production step of coprecipitating, in a non-aqueous solvent, a cobalt-containing compound (a) and a lanthanoid-containing compound (b), which are soluble in the non-aqueous solvent, with a precipitating agent containing the divalent or higher carboxylic acid compound (c), and then obtaining a catalyst from the coprecipitated reaction product.

8. The method for producing an alcohol according to any one of claims 1 to 3, wherein the step 1 comprises the following steps 1a, 1b, and 1c: Step 1a: A step of uniformly dissolving the cobalt-containing compound (a) and the lanthanoid-containing compound (b) in the non-aqueous solvent to obtain a raw material solution. Step 1b: A step of dissolving the precipitant containing the divalent or higher carboxylic acid compound (c) in the non-aqueous solvent to obtain a precipitant solution. Step 1c: A step of mixing the raw material solution obtained in step 1a with the precipitant solution obtained in step 1b to coprecipitate the cobalt-containing compound (a) and the lanthanoid-containing compound (b).

9. The method for producing an alcohol according to claim 8, wherein the step 1c is the following step 1c': Step 1c': A step of adding the precipitant solution obtained in step 1b to the raw material solution obtained in step 1a to coprecipitate the cobalt-containing compound (a) and the lanthanoid-containing compound (b).

10. The method for producing an alcohol according to any one of claims 1 to 3, wherein the step 2 is carried out in a slurry bed reactor.

11. The method includes a step of reacting a cobalt-containing compound (a) and a lanthanoid-containing compound (b), both of which are soluble in the non-aqueous solvent, with a divalent or higher carboxylic acid compound (c) in a non-aqueous solvent, and obtaining a catalyst from the reaction product at 500°C or less, In the step, the amount of the lanthanoid element in the lanthanoid element-containing compound (b) relative to 1 mol of cobalt in the cobalt-containing compound (a) is 0.05 mol or more and 1.20 mol or less; When the lanthanoid element of the lanthanoid element-containing compound (b) is lanthanum, the amounts of the cobalt-containing compound (a) and the lanthanoid element-containing compound (b) blended in the non-aqueous solvent are such that the amount of the lanthanoid element of the lanthanoid element-containing compound (b) relative to 1 mol of cobalt in the cobalt-containing compound (a) is 0.05 mol or more and 0.80 mol or less; When the lanthanoid element of the lanthanoid element-containing compound (b) is cerium, the blending amounts of the cobalt-containing compound (a) and the lanthanoid element-containing compound (b) in the non-aqueous solvent are such that the amount of the lanthanoid element of the lanthanoid element-containing compound (b) relative to 1 mol of cobalt in the cobalt-containing compound (a) is 0.05 mol or more and 0.98 mol or less. A method for producing a catalyst for producing alcohol from synthesis gas.

12. A catalyst obtained from a reaction product of (a) a cobalt-containing compound and (b) a lanthanoid-containing compound, both soluble in the non-aqueous solvent, with (c) a divalent or higher carboxylic acid compound in a non-aqueous solvent at 500°C or less, When obtaining the catalyst, the amount of the lanthanoid element in the lanthanoid element-containing compound (b) relative to 1 mol of cobalt in the cobalt-containing compound (a) is 0.05 mol or more and 1.20 mol or less; When the lanthanoid element of the lanthanoid element-containing compound (b) is lanthanum, the amounts of the cobalt-containing compound (a) and the lanthanoid element-containing compound (b) blended in the non-aqueous solvent are such that the amount of the lanthanoid element of the lanthanoid element-containing compound (b) relative to 1 mol of cobalt in the cobalt-containing compound (a) is 0.05 mol or more and 0.80 mol or less; When the lanthanoid element of the lanthanoid element-containing compound (b) is cerium, the blending amounts of the cobalt-containing compound (a) and the lanthanoid element-containing compound (b) in the non-aqueous solvent are such that the amount of the lanthanoid element of the lanthanoid element-containing compound (b) relative to 1 mol of cobalt in the cobalt-containing compound (a) is 0.05 mol or more and 0.98 mol or less. Use to produce alcohol by reacting carbon monoxide and hydrogen in synthesis gas.

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