How Guerbet alcohols are produced

Abstract

To provide a method of manufacturing high quality Guerbet alcohol with small amount of impurities by suppressing generation of a byproduct ester.SOLUTION: [1] A method of manufacturing Guerbet alcohol by reacting a raw material alcohol having 8 or larger and 22 or smaller carbons under the presence of (A) a catalyst containing the following first component, a second component, and a third component. The first component: copper, the second component: one kind selected from the group consisting of cobalt, nickel, molybdenum, and rhenium, the third component: at least one kind that is an element belonging to the third to tenth, twelfth group of the fourth period of a periodic table, and an element belonging to the third to seventh group and the eleventh to twelfth group of the fifth to sixth period of the periodic table and selected from the group consisting of an element different from the elements selected as the second component.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for producing Guerbet alcohols. [Background technology]

[0002] It has been widely known that aliphatic alcohols are reacted in the presence of a base catalyst or in the presence of a base catalyst and a co-catalyst to remove one molecule of water from two molecules of alcohol, thereby obtaining one molecule of branched dimerized alcohol (Guerbet alcohol), and this reaction is known as the Guerbet reaction.

[0003] Taking the case where a primary alcohol is used as the raw material alcohol as an example, the reaction mechanism of the Guerbet reaction is presumed to consist of the following elementary reactions (1) to (4). (1) Dehydrogenation of alcohol to form aldehyde (2) Formation of α,β-unsaturated aldehydes by aldol condensation of aldehydes (3) Reduction of α,β-unsaturated aldehydes to form allylic alcohols (4) Reduction of allyl alcohol to form Guerbet alcohol

[0004] In the elementary reactions (1) to (4) above, many studies have been conducted and reported on the type and amount of the base catalyst used, the type and amount of the cocatalyst used, and the like, with the aim of suppressing side reactions, increasing the reaction rate, and improving the yield and quality of the Guerbet alcohol produced.

[0005] For example, Patent Document 1 discloses a method for producing a branched dimerized alcohol, in which an alcohol having 3 to 26 carbon atoms is reacted in the presence of (a) a catalyst composed of an alkaline substance and (b) a catalyst selected from copper, a fourth-period transition metal element (chromium, cobalt, nickel, manganese, iron, zinc), and a Group 8 platinum group element (platinum, palladium, ruthenium, rhodium). [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 2-286638 Summary of the Invention [Problem to be solved by the invention]

[0007] However, according to the method for producing a branched dimerized alcohol disclosed in Patent Document 1, it is possible to shorten the reaction time and improve the yield and selectivity of the produced alcohol, but there is still room for improvement from the viewpoint of suppressing side reactions and improving the quality of the Guerbet alcohol.

[0008] The by-products of the elementary reactions (1) to (4) above include esters (hereinafter also referred to as "by-product esters") that have twice the carbon number of the raw material alcohol, i.e., the same carbon number as the resulting Guerbet alcohol. Because the boiling point of these by-product esters is similar to that of the resulting Guerbet alcohol, their removal by distillation is difficult, which has been a problem. Therefore, an object of the present invention is to provide a method for producing high-quality Guerbet alcohols with few impurities, while suppressing the production of by-product esters. [Means for solving the problem]

[0009] The present inventors have found that the above-mentioned problems can be solved by reacting a raw material alcohol having from 8 to 22 carbon atoms in the presence of a specific catalyst (A). That is, the present invention provides the following [1] and [2]. [1] A method for producing Guerbet alcohols, comprising reacting a raw material alcohol having 8 to 22 carbon atoms in the presence of a catalyst (A) containing the following first, second, and third components: First component: copper Second component: one selected from the group consisting of cobalt, nickel, molybdenum, and rhenium Third component: at least one element selected from the group consisting of elements belonging to Groups 3 to 10 and 12 of Period 4 of the Periodic Table, and elements belonging to Groups 3 to 7 and Groups 11 to 12 of Periods 5 and 6 of the Periodic Table, which are different from the element selected as the second component [2] A catalyst used in a method for producing Guerbet alcohol, comprising the following first component, second component, and third component: First component: copper Second component: one selected from the group consisting of cobalt, nickel, molybdenum, and rhenium Third component: at least one element selected from the group consisting of elements belonging to Groups 3 to 10 and 12 of Period 4 of the Periodic Table, and elements belonging to Groups 3 to 7 and Groups 11 to 12 of Periods 5 and 6 of the Periodic Table, which are different from the element selected as the second component [Effects of the Invention]

[0010] According to the present invention, it is possible to provide a method for producing high-quality Guerbet alcohols with few impurities, while suppressing the production of by-product esters. DETAILED DESCRIPTION OF THE INVENTION

[0011] [Raw alcohol] In the method for producing Guerbet alcohol of the present invention, an alcohol having 8 to 22 carbon atoms (hereinafter also simply referred to as "raw material alcohol") is used. From the viewpoint of yield, the carbon number of the raw material alcohol is 8 or more, preferably 9 or more, more preferably 10 or more, and 22 or less, preferably 20 or less, more preferably 18 or less. The raw material alcohols can be used alone or in combination of two or more.

[0012] Examples of the raw material alcohol include primary aliphatic alcohols and secondary aliphatic alcohols. Among these, from the viewpoint of yield, primary aliphatic alcohols are preferred, and among these, primary aliphatic alcohols having from 8 to 18 carbon atoms are preferred, with saturated linear primary aliphatic alcohols having from 8 to 18 carbon atoms being more preferred.

[0013] Specific examples of primary aliphatic alcohols include 1-octanol (C8), 1-nonanol (C9), 1-decanol (C10), 1-undecanol (C11), 1-dodecanol (C12), 1-tridecanol (C13), 1-tetradecanol (C14), 1-pentadecanol (C15), 1-hexadecanol (C16), 1-heptadecanol (C17), 1-octadecanol (C18), Examples include saturated linear alcohols such as 1-nonadecanol (C19), 1-eicosanol (C20), 1-heneicosanol (C21), and 1-docosanol (C22); saturated alicyclic alcohols such as cyclohexaneethanol (C8), cyclohexanepropanol (C9), and cyclohexanebutanol (C10); and unsaturated alcohols such as citronellol (C10) and oleyl alcohol (C18).

[0014] Specific examples of secondary aliphatic alcohols include saturated linear alcohols such as 2-octanol (C8), 2-nonanol (C9), 2-decanol (C10), 2-undecanol (C11), 2-dodecanol (C12), 2-tridecanol (C13), 2-tetradecanol (C14), 2-pentadecanol (C15), 2-hexadecanol (C16), 2-heptadecanol (C17), 2-octadecanol (C18), 2-nonadecanol (C19), 2-eicosanol (C20), 2-heneicosanol (C21), and 2-docosanol (C22).

[0015] [Catalyst (A)] The method for producing Guerbet alcohol of the present invention uses a catalyst (A) containing a specific component, but a catalyst (A) in which the specific component is supported on a carrier may also be used. Use of the catalyst (A) suppresses the production of by-product esters and enables the production of high-quality Guerbet alcohol with few impurities.

[0016] The catalyst (A) used in the present invention is a catalyst containing the following first component, second component, and third component, but may also be a catalyst in which the following first component, second component, and third component are supported on a carrier. First component: copper Second component: one selected from the group consisting of cobalt, nickel, molybdenum, and rhenium Third component: at least one element selected from the group consisting of elements belonging to Groups 3 to 10 and 12 of Period 4 of the Periodic Table, and elements belonging to Groups 3 to 7 and Groups 11 to 12 of Periods 5 and 6 of the Periodic Table, which are different from the element selected as the second component

[0017] (1st component) The first component of the catalyst (A) is not particularly limited as long as it is copper (Cu), but may be an oxide.

[0018] The content of the first component (Cu) contained in the catalyst (A) is preferably 0.5 mass% or more, more preferably 1 mass% or more, and even more preferably 3 mass% or more, from the viewpoint of yield, and is preferably 45 mass% or less, more preferably 39 mass% or less, and even more preferably 36 mass% or less, from the viewpoint of yield and economic efficiency. The content of the first component contained in the catalyst (A) can be determined by measurement using the method described in the Examples.

[0019] From the viewpoint of yield, the average primary particle size of the first component (Cu) contained in the catalyst (A) is preferably 0.2 nm or more, more preferably 1 nm or more, even more preferably 3 nm or more, and preferably 50 nm or less, more preferably 40 nm or less, even more preferably 30 nm or less. The average primary particle size of the first component (Cu) contained in the catalyst (A) can be determined by measurement using the method described in the Examples.

[0020] (Second component) The second component of the catalyst (A) is not particularly limited as long as it is one selected from the group consisting of cobalt (Co), nickel (Ni), molybdenum (Mo), and rhenium (Re), but may also be an oxide. Among these second components, one selected from the group consisting of cobalt (Co), nickel (Ni), and rhenium (Re) is preferred from the viewpoints of yield and selectivity.

[0021] The content of the second component contained in the catalyst (A) is preferably 0.5% by mass or more, more preferably 1% by mass or more, and even more preferably 2% by mass or more, from the viewpoint of selectivity, and is preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 20% by mass or less, from the viewpoint of yield. The content of the second component contained in the catalyst (A) can be determined by measurement using the method described in the Examples.

[0022] (third component) The third component of catalyst (A) is not particularly limited as long as it is at least one element selected from the group consisting of elements belonging to Groups 3 to 10 and 12 of Period 4 of the Periodic Table, and elements belonging to Groups 3 to 7 and Groups 11 to 12 of Periods 5 and 6 of the Periodic Table, and which are different from the element selected as the second component, but may also be an oxide.

[0023] Examples of elements belonging to groups 3 to 10 and 12 of the fourth period of the periodic table include scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), and zinc (Zn). Examples of elements belonging to groups 3 to 7 and groups 11 to 12 of the fifth period of the periodic table include yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), silver (Ag), and cadmium (Cd). Examples of elements belonging to groups 3 to 7 and groups 11 to 12 of the sixth period of the periodic table include lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), hafnium (Hf), tantalum (Ta), tungsten (W), rhenium (Re), gold (Au), and mercury (Hg).

[0024] Among these third components, from the viewpoint of yield and selectivity, at least one selected from the group consisting of titanium (Ti), iron (Fe), zinc (Zn), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), lanthanum (La), cerium (Ce), samarium (Sm), tantalum (Ta), tungsten (W), rhenium (Re), and gold (Au) is preferred.

[0025] Among the third components, at least one selected from the group consisting of elements belonging to groups 3 to 7 of periods 4 to 6 of the periodic table is preferred from the viewpoint of selectivity and / or yield. Examples of elements belonging to the third to seventh elements of the fourth period of the periodic table include scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), and manganese (Mn). Examples of elements belonging to elements 3 to 7 of the fifth period of the periodic table include yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), and technetium (Tc). Examples of elements belonging to the third to seventh rows of the sixth period of the periodic table include lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), hafnium (Hf), tantalum (Ta), tungsten (W), and rhenium (Re). Among the third components, from the viewpoint of selectivity, at least one selected from the group consisting of titanium (Ti), yttrium (Y), niobium (Nb), molybdenum (Mo), lanthanum (La), cerium (Ce), samarium (Sm), tantalum (Ta), tungsten (W), and rhenium (Re) is preferred, and among these, at least one selected from the group consisting of titanium (Ti), yttrium (Y), molybdenum (Mo), lanthanum (La), cerium (Ce), samarium (Sm), tantalum (Ta), and rhenium (Re) is more preferred. Among the third components, from the viewpoint of yield, at least one selected from the group consisting of titanium (Ti), yttrium (Y), zirconium (Zr), niobium (Nb), lanthanum (La), cerium (Ce), samarium (Sm), tantalum (Ta), and tungsten (W) is preferred. Among the third components, from the viewpoints of yield and selectivity, at least one selected from the group consisting of titanium (Ti), yttrium (Y), niobium (Nb), lanthanum (La), cerium (Ce), samarium (Sm), tantalum (Ta), and tungsten (W) is preferred.

[0026] The content of the third component contained in the catalyst (A) is preferably 0.1 mass% or more, more preferably 0.3 mass% or more, and even more preferably 0.5 mass% or more, from the viewpoint of yield and selectivity, and is preferably 15 mass% or less, more preferably 10 mass% or less, and even more preferably 5 mass% or less, from the viewpoint of yield. The content of the third component contained in the catalyst (A) can be determined by measurement using the method described in the Examples.

[0027] In the catalyst (A), the molar ratio of the amount of the second component to the amount of the first component is, from the viewpoint of yield, preferably 0.01 or more, more preferably 0.03 or more, even more preferably 0.04 or more, still more preferably 0.05 or more, still more preferably 0.13 or more, still more preferably 0.16 or more, and is preferably 10 or less, more preferably 9 or less, still more preferably 6 or less, still more preferably 5 or less, still more preferably 2 or less, and still more preferably 1 or less.

[0028] In the catalyst (A), the molar ratio of the amount of the third component to the amount of the first component is, from the viewpoint of yield, preferably 0.0003 or more, more preferably 0.001 or more, even more preferably 0.003 or more, still more preferably 0.007 or more, still more preferably 0.01 or more, and is preferably 0.8 or less, more preferably 0.7 or less, even more preferably 0.6 or less, and still more preferably 0.5 or less.

[0029] The catalyst (A) may contain elements other than the first component, the second component and the third component, as long as the effects of the present invention are not impaired.

[0030] (Carrier) The carrier for the catalyst (A) is not particularly limited as long as it can support the first component, the second component, and the third component. Examples of the support for catalyst (A) include carbon materials such as activated carbon, nanocarbon, and carbon black; and inorganic materials such as aluminum oxide, iron oxide, copper oxide, titanium oxide, zirconium oxide, zeolite, cerium oxide, and hydrotalcite. Among these, from the viewpoints of versatility and economy, the support for catalyst (A) is preferably at least one selected from the group consisting of aluminum oxide, activated carbon, titanium oxide, zirconium oxide, zeolite, cerium oxide, and hydrotalcite, and more preferably at least one selected from the group consisting of aluminum oxide, zirconium oxide, and hydrotalcite. The shape of the carrier is not particularly limited, and is usually a powder, the median diameter (d50) of which is usually 1 to 300 μm, but may be in other shapes derived from powder as needed.

[0031] The amounts of the first to third components supported on the carrier (supported amounts) relative to 100% by mass of the catalyst (A) are preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more from the viewpoint of yield, and are preferably 60% by mass or less, more preferably 50% by mass or less, and even more preferably 45% by mass or less from the viewpoints of yield and economy. Here, "the amounts of the first to third components supported on the carrier (supported amounts) in 100 mass % of the catalyst (A)" means the total content of the first to third components contained in the catalyst (A).

[0032] The mass ratio of the second component to the first component in the catalyst (A) is preferably 0.10 or more, more preferably 0.12 or more, and even more preferably 0.15 or more, from the viewpoint of selectivity, and is preferably 9 or less, more preferably 5 or less, and even more preferably 1 or less, from the viewpoint of yield.

[0033] The mass ratio of the third component to the first component in the catalyst (A) is preferably 0.001 or more, more preferably 0.005 or more, and even more preferably 0.01 or more, from the viewpoint of yield and selectivity, and is preferably 0.60 or less, more preferably 0.50 or less, and even more preferably 0.40 or less, from the viewpoint of yield.

[0034] The shape of the catalyst (A) is not particularly limited, and examples thereof include powder, granules, noodles, pellets, etc. Granules, noodles, pellets, etc. can be produced by granulating and molding the powder catalyst (A) by a known method.

[0035] When the catalyst (A) is a powder, the median diameter (d50) of the catalyst (A) is preferably 1 μm or more, more preferably 3 μm or more, even more preferably 5 μm or more, and even more preferably 7 μm or more from the viewpoint of ease of recovery, and is preferably 300 μm or less, more preferably 200 μm or less, even more preferably 100 μm or less, and even more preferably 30 μm or less from the viewpoint of yield. Here, the median diameter (d50) of the catalyst (A) can be determined using a laser diffraction / scattering particle size distribution analyzer "LA-920" (manufactured by Horiba, Ltd.). The measurement is performed by dispersing 0.05 g of the catalyst (A) in ion-exchanged water, which is the measurement solvent, with stirring (stirring speed: level 4), and calculating the median diameter (d50) using an appropriate relative refractive index.

[0036] When the catalyst (A) is granular, the average particle size of the catalyst (A) is preferably 0.2 mm or more, more preferably 0.4 mm or more, and even more preferably 0.6 mm or more from the viewpoint of ease of recovery, and is preferably 2.0 mm or less, more preferably 1.3 mm or less, and even more preferably 0.8 mm or less from the viewpoint of yield. Here, the average particle size of the catalyst (A) refers to the arithmetic mean particle size, which can be determined using a vernier caliper. The number of granules used to determine the average particle size may be 30 randomly selected granules.

[0037] When the catalyst (A) is in the form of noodles, the average diameter of the catalyst (A) is preferably 1.0 mm or more, more preferably 1.2 mm or more, and even more preferably 1.4 mm or more from the viewpoint of catalyst strength, and is preferably 2.5 mm or less, more preferably 2.0 mm or less, and even more preferably 1.5 mm or less from the viewpoint of yield. Here, the average diameter of the catalyst (A) refers to the arithmetic mean diameter, which can be determined using a vernier caliper. The number of noodles used to determine the average diameter may be 30 noodles selected at random.

[0038] When the catalyst (A) is in the form of noodles, the average length of the catalyst (A) is preferably 2 mm or more, more preferably 3 mm or more, from the viewpoint of catalyst strength, and is preferably 8 mm or less, more preferably 6 mm or less, and even more preferably 4 mm or less, from the viewpoint of uniformity during packing and yield. Here, the average length of the catalyst (A) refers to the arithmetic mean length, which can be determined using a vernier caliper. The number of noodles used to determine the average length may be 30 noodles selected at random.

[0039] When the catalyst (A) is in the form of pellets, the average diameter and height of the catalyst (A) are preferably 1.5 mm or more, more preferably 2.0 mm or more, and even more preferably 2.5 mm or more from the viewpoint of catalyst strength, and are preferably 5.0 mm or less, more preferably 4.0 mm or less, and even more preferably 3.0 mm or less from the viewpoint of yield. Here, the average diameter and average height of the catalyst (A) refer to the arithmetic mean diameter and arithmetic mean height, and can be determined using a vernier caliper. The number of pellets used to determine the average diameter or height may be 30 randomly selected pellets.

[0040] (Preparation of catalyst (A)) The catalyst (A) used in the present invention can be prepared by known methods such as precipitation, impregnation, ion exchange, alloying, and adsorption. The catalyst (A) can be preferably prepared by a method in which the first and second components are supported on a carrier by a precipitation method, and then the third component is supported on the carrier supporting the first and second components by an impregnation method. The precipitation method for supporting the first and second components on the carrier can be carried out, for example, by the following method. A water-soluble salt containing the first component and a water-soluble salt containing the second component are dissolved in ion-exchanged water to prepare a mixed aqueous solution containing the first and second components. Separately, an alkaline aqueous solution containing an alkaline component such as sodium carbonate and a slurry containing a component that will serve as a carrier, such as zirconium oxide, are prepared. Next, the mixed aqueous solution containing the first and second components is added dropwise to the slurry, and simultaneously the alkaline aqueous solution is added dropwise for a predetermined time while maintaining the slurry at a predetermined pH at which the first and second components are insolubilized and precipitated as carbonates or hydroxides, thereby obtaining a solid content in which the carbonates or hydroxides of the first and second components are attached to the carrier. This solid content is then repeatedly filtered and washed, and then calcined at a predetermined temperature for a predetermined time to obtain a calcined product in which the first and second components are supported on the carrier. The impregnation method for causing the carrier carrying the first and second components to carry the third component can be carried out, for example, by the following method. The third component-containing compound is dissolved in an organic solvent or water, and a calcined solid product of the first and second components supported on a carrier is added thereto. The mixture is concentrated, for example, by stirring under reduced pressure or heating, until the liquid disappears. The mixture is then dried at a predetermined temperature and further calcined at a predetermined temperature for a predetermined time, thereby obtaining catalyst (A), which is a calcined product of the first to third components supported on a carrier.

[0041] The calcination temperature for obtaining the calcined product in which the first and second components are supported on a carrier and the calcined product in which the first to third components are supported on a carrier is, from the viewpoint of the yield of Guerbet alcohol, 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 850°C or lower, even more preferably 800°C or lower.

[0042] The calcination time for obtaining the calcined product in which the first and second components are supported on a carrier, and the calcined product in which the first to third components are supported on a carrier, is preferably 1 hour or more, more preferably 2 hours or more, even more preferably 3 hours or more, from the viewpoint of the yield of Guerbet alcohol, and is preferably 10 hours or less, more preferably 7 hours or less, even more preferably 5 hours or less.

[0043] The calcination atmosphere for obtaining the calcined product in which the first and second components are supported on a carrier and the calcined product in which the first to third components are supported on a carrier is not particularly limited, but examples thereof include an inert gas atmosphere such as nitrogen, an oxidizing atmosphere such as air, and a reducing atmosphere such as hydrogen. Among these, an oxidizing atmosphere such as air is preferred from the viewpoint of the yield of Guerbet alcohol. The calcination atmosphere may be sealed or may be circulated.

[0044] [Base catalyst (B)] In the method for producing Guerbet alcohol of the present invention, it is preferable to use a base catalyst (B) together with the catalyst (A). By using the basic catalyst (B) together with the catalyst (A), it becomes easier to suppress the production of by-product esters, and it becomes easier to produce high-quality Guerbet alcohols with fewer impurities.

[0045] Examples of the base catalyst (B) include alkali metals or alkaline earth metals, as well as hydrides, hydroxides, carbonates, hydrogencarbonates, and alkoxides thereof. Specific examples of alkali metal or alkaline earth metal hydrides, hydroxides, carbonates, bicarbonates, and alkoxide compounds include alkali metal hydroxides such as LiOH, NaOH, KOH, RbOH, and CsOH; alkali metal carbonates such as Li2CO3, Na2CO3, K2CO3, Rb2CO3, and Cs2CO3; alkali metal bicarbonates such as LiHCO3, NaHCO3, KHCO3, RbHCO3, and CsHCO3; alkali metal alkoxide compounds such as sodium methoxide, sodium ethoxide, sodium t-butoxide, potassium methoxide, potassium ethoxide, and potassium t-butoxide; and alkaline earth metal hydroxides such as Mg(OH)2 and Ca(OH)2. Among the above-mentioned base catalysts (B), from the viewpoint of yield, alkali metal hydroxides, which are strong bases, such as LiOH, NaOH, KOH, RbOH, and CsOH; and alkali metal alkoxide compounds, such as sodium methoxide, sodium ethoxide, sodium t-butoxide, potassium methoxide, potassium ethoxide, and potassium t-butoxide, are preferred, and among these, NaOH and KOH are more preferred from the viewpoints of versatility and economy. The base catalyst (B) can be used alone or in combination of two or more. The base catalyst (B) may not be supported on a carrier.

[0046] The amount of the base catalyst (B) is, relative to the total amount of the raw material alcohols, preferably 0.05 mol % or more, more preferably 0.1 mol % or more, and even more preferably 0.2 mol % or more, from the viewpoint of yield, and is preferably 7 mol % or less, more preferably 5 mol % or less, and even more preferably 3 mol % or less, from the viewpoint of selectivity.

[0047] [Guerbet reaction] In the method for producing Guerbet alcohol of the present invention, a raw material alcohol having a carbon number of 8 to 22 is reacted (dehydration condensation reaction (Guerbet reaction)) in the presence of a catalyst (A) containing a specific component and / or a catalyst (A) in which the specific component is supported on a carrier, to produce a Guerbet alcohol.

[0048] The reaction format of the Guerbet reaction is not particularly limited, and may be a suspension bed reaction or a fixed bed reaction, which can be appropriately selected depending on the catalytic activity, reaction scale, etc. The material of the reaction apparatus used in the Guerbet reaction may be stainless steel (SUS201, SUS202, SUS301, SUS302, SUS303, SUS304, SUS305, SUS316, SUS317, SUS329J1, SUS403, SUS405, SUS420, SUS430, SUS430LX, SUS630) or glass.

[0049] The method for producing Guerbet alcohol of the present invention may be any of a batch system, a semi-batch system, and a continuous system. When the reaction type is a suspension bed reaction, a batch or semi-batch system is preferred from the viewpoint of operability, and the amount of catalyst (A) is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more, based on the total amount of raw material alcohols, from the viewpoint of yield, and is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 1% by mass or less, from the viewpoint of economy. When the reaction type is a fixed bed reaction, a continuous system is preferred from the viewpoint of productivity, and the amount of catalyst (A) is, from the viewpoint of yield, preferably 10% by mass or more, more preferably 15% by mass or more, even more preferably 25% by mass or more, and still more preferably 50% by mass or more, relative to the total amount of raw material alcohols, and, from the viewpoint of economy, is preferably 4000% by mass or less, more preferably 2500% by mass or less, even more preferably 1000% by mass or less, and still more preferably 500% by mass or less.

[0050] The reaction temperature in the Guerbet reaction is appropriately determined taking into consideration the boiling point of the raw material alcohol, but from the viewpoint of yield, it is preferably 180°C or higher, more preferably 190°C or higher, even more preferably 200°C or higher, and even more preferably 220°C or higher, and from the viewpoint of selectivity, it is preferably 300°C or lower, more preferably 280°C or lower, and even more preferably 260°C or lower. The reaction time in the Guerbet reaction is determined appropriately depending on the reaction temperature and the type of raw material alcohol, but in a suspended bed reaction, it is usually 1 hour or more from the viewpoint of yield, and preferably 20 hours or less, more preferably 10 hours or less, from the viewpoint of productivity. The LHSV (liquid hourly space velocity) in a fixed bed reaction is preferably 10 / hr or less, more preferably 7 / hr or less, even more preferably 5 / hr or less, still more preferably 3 / hr or less, from the viewpoint of yield, and is preferably 0.03 / hr or more, more preferably 0.05 / hr or more, even more preferably 0.1 / hr or more, still more preferably 0.2 / hr or more, from the viewpoint of productivity. The pressure of the gas phase during the Guerbet reaction may be reduced, normal, or increased. From the viewpoints of yield and selectivity, the pressure may be reduced, and from the viewpoints of operability and production costs, the pressure may be normal.

[0051] In the Guerbet reaction, from the viewpoints of yield and selectivity, it is preferable to introduce an inert gas into the reaction system and circulate the inert gas as a carrier. The inert gas is not particularly limited, but examples thereof include nitrogen gas, argon gas, and carbon dioxide gas, and among these, nitrogen gas is preferably used. The inert gas can be passed through the reaction solution by passing it above the reaction solution or by bubbling it through the reaction solution. The flow rate of the inert gas during the temperature increase until the reaction temperature is reached is not particularly limited, but from the viewpoints of yield and selectivity, it is preferably 0.5 L / hr or more, more preferably 3 L / hr or more, and even more preferably 8 L / hr or more per kg of reaction solution, and from the viewpoint of economy, it is preferably 30 L / hr or less, more preferably 25 L / hr or less, and even more preferably 20 L / hr or less. The flow rate of the inert gas during the reaction when the reaction temperature has been reached is not particularly limited, but from the viewpoints of yield and selectivity, it is preferably 0.02 L / hr or more, more preferably 0.08 L / hr or more, and even more preferably 0.1 L / hr or more per kg of reaction solution, and from the viewpoint of economy, it is preferably 10 L / hr or less, more preferably 5 L / hr or less, and even more preferably 2 L / hr or less.

[0052] The Guerbet alcohol produced by the production method of the present invention depends on the type of raw material alcohol used, but may be saturated or unsaturated, primary or secondary, or may have a cyclic structure. Furthermore, from the viewpoint of yield, the number of carbon atoms in the Guerbet alcohol produced by the production method of the present invention is preferably 16 or more, more preferably 18 or more, even more preferably 20 or more, and is preferably 44 or less, more preferably 40 or less, even more preferably 36 or less.

[0053] According to the production method of the present invention, the by-production rate of by-product esters (dimer esters) is low and the effect of suppressing the production of by-product esters (dimer esters) is excellent, so that high-quality Guerbet alcohols with few impurities can be obtained. Therefore, the Guerbet alcohols obtained by the production method of the present invention can be used directly for various applications, but can also be purified by distillation or other procedures as necessary. Guerbet alcohols are useful as raw materials or intermediate raw materials for surfactants, textile oils, fabric softeners, cosmetics, pharmaceuticals, lubricants, and the like. From the perspective of use in these applications, the purity of the Guerbet alcohols is preferably 95% by mass or more, more preferably 97% by mass or more, and even more preferably 98% by mass or more.

[0054] In addition to the above-described embodiments, the present invention discloses the following method for producing Guerbet alcohols. <1> A method for producing Guerbet alcohols, comprising reacting a raw material alcohol having 8 to 22 carbon atoms in the presence of a catalyst (A) containing the following first, second, and third components: First component: Copper (Cu) Second component: one selected from the group consisting of cobalt (Co), nickel (Ni), molybdenum (Mo), and rhenium (Re). Third component: at least one element selected from the group consisting of elements belonging to Groups 3 to 10 and 12 of Period 4 of the Periodic Table, and elements belonging to Groups 3 to 7 and Groups 11 to 12 of Periods 5 and 6 of the Periodic Table, which are different from the element selected as the second component <2> The carbon number of the raw material alcohol is preferably 9 or more, more preferably 10 or more, and preferably 20 or less, more preferably 18 or less. <1> A method for producing Guerbet alcohols according to claim 1. <3> The carbon number of the raw material alcohol is preferably 8 or more and 20 or less. <1> or <2> A method for producing Guerbet alcohols according to claim 1. <4> The carbon number of the raw material alcohol is preferably 8 or more and 18 or less. <1> or <2> A method for producing Guerbet alcohols according to claim 1. <5> The carbon number of the raw material alcohol is preferably 9 or more and 20 or less. <1> or <2> A method for producing Guerbet alcohols according to claim 1. <6> The carbon number of the raw material alcohol is preferably 9 or more and 18 or less. <1> or <2> A method for producing Guerbet alcohols according to claim 1. <7> The carbon number of the raw material alcohol is preferably 10 or more and 20 or less. <1> or <2> A method for producing Guerbet alcohols according to claim 1. <8> The carbon number of the raw material alcohol is preferably 10 or more and 18 or less. <1> or <2> A method for producing Guerbet alcohols according to claim 1. <9> The raw material alcohol is preferably a primary aliphatic alcohol. <1> or <2> A method for producing Guerbet alcohols according to claim 1. <10> The raw material alcohol is preferably a primary aliphatic alcohol having from 8 to 18 carbon atoms. <1> or <2> A method for producing Guerbet alcohols according to claim 1. <11> The raw material alcohol is preferably a saturated linear primary aliphatic alcohol having from 8 to 18 carbon atoms. <1> or <2> A method for producing Guerbet alcohols according to claim 1. <12> The content of the first component contained in the catalyst (A) is preferably 0.5% by mass or more, more preferably 1% by mass or more, even more preferably 3% by mass or more, and preferably 45% by mass or less, more preferably 39% by mass or less, even more preferably 36% by mass or less. <1> ~ <11> A method for producing Guerbet alcohol according to any one of the preceding claims. <13> the average primary particle size of the first component contained in the catalyst (A) is preferably 0.2 nm or more, more preferably 1 nm or more, even more preferably 3 nm or more, and preferably 50 nm or less, more preferably 40 nm or less, even more preferably 30 nm or less; <1> ~ <12> A method for producing Guerbet alcohol according to any one of the preceding claims. <14> The second component is preferably one selected from the group consisting of cobalt (Co), nickel (Ni), and rhenium (Re). <1> ~ <13> A method for producing Guerbet alcohol according to any one of the preceding claims. <15> The content of the second component contained in the catalyst (A) is preferably 0.5% by mass or more, more preferably 1% by mass or more, even more preferably 2% by mass or more, and preferably 30% by mass or less, more preferably 25% by mass or less, even more preferably 20% by mass or less. <1> ~ <14> A method for producing Guerbet alcohol according to any one of the preceding claims. <16> The third component is preferably at least one selected from the group consisting of titanium (Ti), iron (Fe), zinc (Zn), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), lanthanum (La), cerium (Ce), samarium (Sm), tantalum (Ta), tungsten (W), rhenium (Re), and gold (Au). <1> ~ <15> A method for producing Guerbet alcohol according to any one of the preceding claims. <17> Among the third components, at least one selected from the group consisting of elements belonging to groups 3 to 7 of periods 4 to 6 of the periodic table is preferred. <1> ~ <15> A method for producing Guerbet alcohol according to any one of the preceding claims. <18> Among the third components, at least one selected from the group consisting of titanium (Ti), yttrium (Y), niobium (Nb), molybdenum (Mo), lanthanum (La), cerium (Ce), samarium (Sm), tantalum (Ta), tungsten (W), and rhenium (Re) is preferred, and among these, at least one selected from the group consisting of titanium (Ti), yttrium (Y), molybdenum (Mo), lanthanum (La), cerium (Ce), samarium (Sm), tantalum (Ta), and rhenium (Re) is more preferred. <17> A method for producing Guerbet alcohols according to claim 1. <19> Among the third components, at least one selected from the group consisting of titanium (Ti), yttrium (Y), zirconium (Zr), niobium (Nb), lanthanum (La), cerium (Ce), samarium (Sm), tantalum (Ta), and tungsten (W) is preferred. <17> A method for producing Guerbet alcohols according to claim 1. <20> Among the third components, at least one selected from the group consisting of titanium (Ti), yttrium (Y), niobium (Nb), lanthanum (La), cerium (Ce), samarium (Sm), tantalum (Ta), and tungsten (W) is preferred. <17> A method for producing Guerbet alcohols according to claim 1. <21> The content of the third component contained in the catalyst (A) is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, even more preferably 0.5% by mass or more, and preferably 15% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less. <1> ~ <20> A method for producing Guerbet alcohol according to any one of the preceding claims. <22> In the catalyst (A), the molar ratio of the amount of the second component to the amount of the first component is preferably 0.01 or more, more preferably 0.03 or more, even more preferably 0.04 or more, still more preferably 0.05 or more, even more preferably 0.13 or more, even more preferably 0.16 or more, and is preferably 10 or less, more preferably 9 or less, even more preferably 6 or less, even more preferably 5 or less, even more preferably 2 or less, and even more preferably 1 or less. <1> ~ <21> A method for producing Guerbet alcohol according to any one of the preceding claims. <23> In the catalyst (A), the molar ratio of the amount of the third component to the amount of the first component is preferably 0.0003 or more, more preferably 0.001 or more, even more preferably 0.003 or more, still more preferably 0.007 or more, even more preferably 0.01 or more, and is preferably 0.8 or less, more preferably 0.7 or less, even more preferably 0.6 or less, and still more preferably 0.5 or less. <1> ~ <22> A method for producing Guerbet alcohol according to any one of the preceding claims. <24> The catalyst (A) is a catalyst in which the first component, the second component, and the third component are supported on a carrier, and the carrier is preferably at least one selected from the group consisting of aluminum oxide, activated carbon, titanium oxide, zirconium oxide, zeolite, cerium oxide, and hydrotalcite, and among these, it is more preferable that the carrier is at least one selected from the group consisting of aluminum oxide, zirconium oxide, and hydrotalcite. <1> ~ <23> A method for producing Guerbet alcohol according to any one of the preceding claims. <25> In 100% by mass of the catalyst (A), the amounts (supported amounts) of the first to third components supported on the carrier are preferably 1% by mass or more, more preferably 3% by mass or more, even more preferably 5% by mass or more, and preferably 60% by mass or less, more preferably 50% by mass or less, even more preferably 45% by mass or less. <24> A method for producing Guerbet alcohols according to claim 1. <26> the mass ratio of the second component to the first component in the catalyst (A) is preferably 0.10 or more, more preferably 0.12 or more, even more preferably 0.15 or more, and is preferably 9 or less, more preferably 5 or less, even more preferably 1 or less; <1> ~ <25> A method for producing Guerbet alcohol according to any one of the preceding claims. <27> the mass ratio of the third component to the first component in the catalyst (A) is preferably 0.001 or more, more preferably 0.005 or more, even more preferably 0.01 or more, and is preferably 0.60 or less, more preferably 0.50 or less, even more preferably 0.40 or less; <1> ~ <26> A method for producing Guerbet alcohol according to any one of the preceding claims. <28> When the catalyst (A) is a powder, the median diameter of the catalyst (A) is preferably 1 μm or more, more preferably 3 μm or more, even more preferably 5 μm or more, still more preferably 7 μm or more, and preferably 300 μm or less, more preferably 200 μm or less, even more preferably 100 μm or less, and still more preferably 30 μm or less. <1> ~ <27> A method for producing Guerbet alcohol according to any one of the preceding claims. <29> When the catalyst (A) is granular, the average particle size of the catalyst (A) is preferably 0.2 mm or more, more preferably 0.4 mm or more, even more preferably 0.6 mm or more, and is preferably 2.0 mm or less, more preferably 1.3 mm or less, even more preferably 0.8 mm or less. <1> ~ <27> A method for producing Guerbet alcohol according to any one of the preceding claims. <30> When the catalyst (A) is a noodle, the average diameter of the catalyst (A) is preferably 1.0 mm or more, more preferably 1.2 mm or more, even more preferably 1.4 mm or more, and is preferably 2.5 mm or less, more preferably 2.0 mm or less, even more preferably 1.5 mm or less. <1> ~ <27> A method for producing Guerbet alcohol according to any one of the preceding claims. <31> When the catalyst (A) is a noodle, the average length of the catalyst (A) is preferably 2 mm or more, more preferably 3 mm or more, and preferably 8 mm or less, more preferably 6 mm or less, and even more preferably 4 mm or less. <1> ~ <27> A method for producing Guerbet alcohol according to any one of the preceding claims. <32> When the catalyst (A) is in the form of pellets, the average diameter and average height of the catalyst (A) are preferably 1.5 mm or more, more preferably 2.0 mm or more, even more preferably 2.5 mm or more, and preferably 5.0 mm or less, more preferably 4.0 mm or less, even more preferably 3.0 mm or less. <1> ~ <27> A method for producing Guerbet alcohol according to any one of the preceding claims. <33> The firing temperature for obtaining the fired product in which the first and second components are supported on a carrier, and the fired product in which the first to third components are supported on a carrier, is preferably 300°C or higher, more preferably 350°C or higher, even more preferably 400°C or higher, and is preferably 900°C or lower, more preferably 850°C or lower, even more preferably 800°C or lower. <24> ~ <32> A method for producing Guerbet alcohol according to any one of the preceding claims. <34> The calcination time for obtaining the calcined product in which the first and second components are supported on a carrier, and the calcined product in which the first to third components are supported on a carrier, is preferably 1 hour or more, more preferably 2 hours or more, even more preferably 3 hours or more, and is preferably 10 hours or less, more preferably 7 hours or less, even more preferably 5 hours or less. <24> ~ <33> A method for producing Guerbet alcohol according to any one of the preceding claims. <35> The firing atmosphere for obtaining the fired product in which the first and second components are supported on a carrier and the fired product in which the first, second, and third components are supported on a carrier is preferably an oxidizing atmosphere. <24> ~ <34> A method for producing Guerbet alcohol according to any one of the preceding claims. <36> A base catalyst (B) is used together with the catalyst (A), and the base catalyst (B) is preferably a strong base such as an alkali metal hydroxide, e.g., LiOH, NaOH, KOH, RbOH, or CsOH; or an alkali metal alkoxide compound, e.g., sodium methoxide, sodium ethoxide, sodium t-butoxide, potassium methoxide, potassium ethoxide, or potassium t-butoxide, and among these, NaOH or KOH is more preferred. <1> ~ <35> A method for producing Guerbet alcohol according to any one of the preceding claims. <37> The base catalyst (B) may not be supported on a carrier. <36> A method for producing Guerbet alcohols according to claim 1. <38> the amount of the base catalyst (B) is preferably 0.05 mol% or more, more preferably 0.1 mol% or more, even more preferably 0.2 mol% or more, and preferably 7 mol% or less, more preferably 5 mol% or less, even more preferably 3 mol% or less, based on the total amount of the raw material alcohols; <1> ~ <37> A method for producing Guerbet alcohol according to any one of the preceding claims. <39> When the reaction type is a suspension bed reaction, a batch or semi-batch reaction is preferred, and the amount of the catalyst (A) is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 0.1% by mass or more, and preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 1% by mass or less, based on the total amount of the raw material alcohols. <1> ~ <38> A method for producing Guerbet alcohol according to any one of the preceding claims. <40> When the reaction type is a fixed bed reaction, a continuous type is preferred, and the amount of the catalyst (A) is preferably 10% by mass or more, more preferably 15% by mass or more, even more preferably 25% by mass or more, still more preferably 50% by mass or more, and is preferably 4000% by mass or less, more preferably 2500% by mass or less, even more preferably 1000% by mass or less, and still more preferably 500% by mass or less, based on the total amount of the raw material alcohols. <1> ~ <38> A method for producing Guerbet alcohol according to any one of the preceding claims. <41> The reaction temperature is preferably 180°C or higher, more preferably 190°C or higher, even more preferably 200°C or higher, and even more preferably 220°C or higher, and is preferably 300°C or lower, more preferably 280°C or lower, and even more preferably 260°C or lower. <1> ~ <40> A method for producing Guerbet alcohol according to any one of the preceding claims. <42> The reaction time in a suspended bed reaction is preferably 20 hours or less, more preferably 10 hours or less, and the LHSV (liquid hourly space velocity) in a fixed bed reaction is preferably 10 / hr or less, more preferably 7 / hr or less, even more preferably 5 / hr or less, still more preferably 3 / hr or less, and is preferably 0.03 / hr or more, more preferably 0.05 / hr or more, even more preferably 0.1 / hr or more, and still more preferably 0.2 / hr or more. <1> ~ <41> A method for producing Guerbet alcohol according to any one of the preceding claims. <43> The reaction is preferably carried out by introducing an inert gas into the reaction system and circulating the inert gas as a carrier. <1> ~ <42> A method for producing Guerbet alcohol according to any one of the preceding claims. <44> The inert gas is nitrogen gas. <43> A method for producing Guerbet alcohols according to claim 1. <45> the flow rate of the inert gas during heating to the reaction temperature is preferably 0.5 L / hr or more, more preferably 3 L / hr or more, even more preferably 8 L / hr or more, and is preferably 30 L / hr or less, more preferably 25 L / hr or less, even more preferably 20 L / hr or less, per 1 kg of reaction solution; <43> or <44> A method for producing Guerbet alcohols according to claim 1. <46> The flow rate of the inert gas during the reaction when the reaction temperature is reached is preferably 0.02 L / hr or more, more preferably 0.08 L / hr or more, even more preferably 0.1 L / hr or more, per 1 kg of reaction solution, and is preferably 10 L / hr or less, more preferably 5 L / hr or less, even more preferably 2 L / hr or less. <43> ~ <45> A method for producing Guerbet alcohol according to any one of the preceding claims. <47> The carbon number of the Guerbet alcohol is preferably 16 or more, more preferably 18 or more, even more preferably 20 or more, and is preferably 44 or less, more preferably 40 or less, even more preferably 36 or less. <1> ~ <46> A method for producing Guerbet alcohol according to any one of the preceding claims. <48> The purity of the Guerbet alcohol is preferably 95% by mass or more, more preferably 97% by mass or more, and even more preferably 98% by mass or more. <1> ~ <47> A method for producing Guerbet alcohol according to any one of the preceding claims. [Example]

[0055] The present invention will now be described in more detail with reference to examples, but is not limited to these. Various measurements and evaluations in the Preparation Examples, Comparative Preparation Examples, Examples, and Comparative Examples were carried out as follows.

[0056] (1) Measurement by ICP atomic emission spectrometry The elements contained in the catalysts obtained in the Preparation Examples and Comparative Preparation Examples were quantified by ICP optical emission spectrometry (inductively coupled plasma optical emission spectrometry: ICP-AES, ICP-OES) using an ICP optical emission spectrometry analyzer (manufactured by Thermo Fisher Scientific, product name: iCAP6500Duo).

[0057] (2) Measurement of the average primary particle size of Cu The average primary particle size of Cu supported on the carrier contained in the catalysts obtained in the Preparation Examples and Comparative Preparation Examples was measured by the pulse method using a catalyst analyzer (BEL Japan, product name: BELCAT-B). Pretreatment involved reducing CuO under a 5% H2 / Ar gas flow at 150°C for 4 hours, followed by introducing 5% N2O / He gas at 50°C until saturation was reached, and the average primary particle size of Cu was measured from the total gas consumption.

[0058] (3) Measurement of raw material alcohol conversion rate and dimeric ester by-production rate In the examples and comparative examples, the solution after completion of the reaction was diluted with hexane and then analyzed by gas chromatography [column: Ultra ALLOY-1 (MS / HT) capillary column 30.0 m × 250 μm (manufactured by Frontier Laboratories), detector: FID, injection temperature: 300°C, detector temperature: 300°C, He flow rate: 4.6 mL / min.] to quantify the product. The raw material alcohol conversion rate and the dimer ester by-product rate were calculated from the results of gas chromatography using the following formulas. The results are shown in Tables 1 to 4. Raw material alcohol conversion rate (%) = 100 - [amount of remaining raw material alcohol (mol) / amount of raw material alcohol charged (mol)] × 100 Dimer ester by-production rate (%) = [amount of dimer ester produced (moles) × 2 / amount of raw material alcohol charged (moles)] × 100 When 1-dodecanol (C12) is used as the raw material alcohol, the dimer ester is a C24 ester, when 1-decanol (C10) is used, the dimer ester is a C20 ester, and when 1-octadecanol (C18) is used, the dimer ester is a C36 ester.

[0059] (Preparation example A) <Preparation of CuNi / ZrO2 by precipitation method> A 300 mL beaker was charged with 50 g of copper nitrate trihydrate (Kanto Chemical Co., Inc.) and 13 g of nickel nitrate hexahydrate (Kanto Chemical Co., Inc.), and 260 g of ion-exchanged water was added to dissolve the mixture. This prepared a copper nitrate and nickel nitrate mixed aqueous solution with a Cu:Ni ratio of 5:1 (by mass). Next, a separate 300 mL beaker was charged with 48 g of sodium carbonate (Fujifilm Wako Pure Chemical Industries, Ltd.), and 269 g of ion-exchanged water was added to dissolve the mixture. A separate 2 L beaker was charged with 50 g of zirconium oxide (Daiichi Kigenso Kagaku Kogyo Co., Ltd., product name: RC-100 zirconium oxide (white powder, median diameter (d50): 1.5-4 μm)) and 875 g of ion-exchanged water was added to prepare a zirconium oxide slurry. The copper nitrate and nickel nitrate mixed aqueous solution was added dropwise to the zirconium oxide slurry over 80 minutes while maintaining the pH at 7 (35°C), and simultaneously the sodium carbonate aqueous solution was added dropwise. After the addition was completed, the solid content of Cu and Ni carbonates or hydroxides adhering to the zirconium oxide support was filtered under reduced pressure, and the resulting cake was washed with 1 L of ion-exchanged water. The cake was reslurried, filtered under reduced pressure, and washed four times, then dried at 120°C for 18 hours and calcined in air at 500°C for 3 hours to obtain a CuNi / ZrO2 calcined product. (Preparation Example 1) <Preparation of CuNiTi / ZrO2 by impregnation method> 0.36 g of titanium tetraisopropoxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was placed in a 50 mL recovery flask, and 4.7 g of 2-propanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added to completely dissolve the titanium tetraisopropoxide. 2.0 g of the calcined CuNi / ZrO2 product obtained in Preparation Example A was added, and the mixture was concentrated using a rotary evaporator until the liquid was gone. The mixture was then dried at 120°C for 18 hours and calcined in air at 500°C for 3 hours to obtain a calcined CuNiTi / ZrO2 product (powder) that was used as catalyst (A). The average primary particle size of Cu contained in the obtained fired product was 21 nm.

[0060] (Preparation Example 2) <Preparation of CuNiZn / ZrO2 by Impregnation Method> In the preparation of CuNiTi / ZrO2 by the impregnation method of Preparation Example 1, 0.36 g of titanium tetraisopropoxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was changed to 0.27 g of zinc nitrate hexahydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and the solvent was changed from 4.7 g of 2-propanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) to 6 g of ion-exchanged water. The same operations as in Preparation Example 1 were carried out to obtain a calcined product (powder) of CuNiZn / ZrO2, which is catalyst (A).

[0061] (Preparation Example 3) <Preparation of CuNiY / ZrO2 by impregnation method> In the preparation of CuNiZn / ZrO2 by the impregnation method of Preparation Example 2, except that 0.27 g of zinc nitrate hexahydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was changed to 0.19 g of yttrium nitrate n-hydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), the same procedure as in Preparation Example 2 was carried out to obtain a CuNiY / ZrO2 calcined product (powder) as catalyst (A). The average primary particle size of Cu contained in the obtained fired product was 16 nm.

[0062] (Preparation Example 4) <Preparation of CuNiZr / ZrO2 by Impregnation Method> In the preparation of CuNiZn / ZrO2 by the impregnation method of Preparation Example 2, except that 0.27 g of zinc nitrate hexahydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was changed to 0.18 g of zirconyl nitrate dihydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), the same procedure as in Preparation Example 2 was carried out to obtain a calcined product (powder) of CuNiZr / ZrO2, which is catalyst (A).

[0063] (Preparation Example 5) <Preparation of CuNiNb / ZrO2 by impregnation method> In the preparation of CuNiZn / ZrO2 by the impregnation method of Preparation Example 2, except that 0.27 g of zinc nitrate hexahydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was changed to 0.20 g of ammonium niobium oxalate (manufactured by Sigma-Aldrich Japan LLC), the same procedure as in Preparation Example 2 was carried out to obtain a calcined product (powder) of CuNiNb / ZrO2, which is catalyst (A). The average primary particle size of Cu contained in the obtained fired product was 16 nm.

[0064] (Preparation Example 6) <Preparation of CuNiLa / ZrO2 by impregnation method> In the preparation of CuNiZn / ZrO2 by the impregnation method of Preparation Example 2, except that 0.27 g of zinc nitrate hexahydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was changed to 0.19 g of lanthanum nitrate hexahydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), the same procedure as in Preparation Example 2 was carried out to obtain a calcined product (powder) of CuNiLa / ZrO2, which is catalyst (A). The average primary particle size of Cu contained in the obtained fired product was 17 nm.

[0065] (Preparation Example 7) <Preparation of CuNiCe / ZrO2 by Impregnation Method> In the preparation of CuNiZn / ZrO2 by the impregnation method of Preparation Example 2, except that 0.27 g of zinc nitrate hexahydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was changed to 0.19 g of cerium nitrate hexahydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), the same procedure as in Preparation Example 2 was carried out to obtain a calcined product (powder) of CuNiCe / ZrO2, which is catalyst (A). The average primary particle size of Cu contained in the obtained fired product was 17 nm.

[0066] (Preparation Example 8) <Preparation of CuNiSm / ZrO2 by impregnation method> In the preparation of CuNiZn / ZrO2 by the impregnation method of Preparation Example 2, except that 0.27 g of zinc nitrate hexahydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was changed to 0.15 g of samarium chloride hexahydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), the same procedure as in Preparation Example 2 was carried out to obtain a calcined product (powder) of CuNiSm / ZrO2, which is catalyst (A).

[0067] (Preparation Example 9) <Preparation of CuNiTa / ZrO2 by impregnation method> In the preparation of CuNiTi / ZrO2 by the impregnation method of Preparation Example 1, 0.36 g of titanium tetraisopropoxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was changed to 0.12 g of tantalum chloride (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and the solvent was changed from 4.7 g of 2-propanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) to 4.7 g of ethanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), but the same operations as in Preparation Example 1 were carried out to obtain a CuNiTa / ZrO2 calcined product (powder) as catalyst (A).

[0068] (Preparation Example 10) <Preparation of CuNiW / ZrO2 by impregnation method> In the preparation of CuNiZn / ZrO by the impregnation method of Preparation Example 2, 0.27 g of zinc nitrate hexahydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was changed to 0.08 g of tungstic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), the solvent ion-exchanged water was changed from 6 g to 16 g, and a 28% aqueous ammonia solution (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added to the 16 g of ion-exchanged water until the pH reached 8. The same operation as in Preparation Example 2 was performed to obtain a CuNiW / ZrO calcined product (powder) as catalyst (A). The average primary particle size of Cu contained in the obtained fired product was 20 nm.

[0069] (Preparation Example 11) <Preparation of CuNiAu / ZrO2 by impregnation method> In the preparation of CuNiZn / ZrO2 by the impregnation method of Preparation Example 2, except that 0.27 g of zinc nitrate hexahydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was changed to 0.13 g of tetrachloroauric acid tetrahydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), the same procedure as in Preparation Example 2 was carried out to obtain a calcined product (powder) of CuNiAu / ZrO2, which is catalyst (A).

[0070] (Preparation Example 12) <Preparation of CuNiFe / ZrO2 by impregnation method> In the preparation of CuNiZn / ZrO2 by the impregnation method of Preparation Example 2, except that 0.27 g of zinc nitrate hexahydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was changed to 0.43 g of iron nitrate nonahydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), the same procedure as in Preparation Example 2 was carried out to obtain a calcined product (powder) of CuNiFe / ZrO2, which is catalyst (A).

[0071] (Preparation Example 13) <Preparation of CuNiMo / ZrO2 by impregnation method> In the preparation of CuNiZn / ZrO2 by the impregnation method of Preparation Example 2, except that 0.27 g of zinc nitrate hexahydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was changed to 0.11 g of ammonium molybdate tetrahydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), the same procedure as in Preparation Example 2 was carried out to obtain a calcined product (powder) of CuNiMo / ZrO2, which is catalyst (A).

[0072] (Preparation Example 14) <Preparation of CuNiRe / ZrO2 by impregnation method> In the preparation of CuNiZn / ZrO2 by the impregnation method of Preparation Example 2, the same procedure as in Preparation Example 2 was carried out, except that 0.27 g of zinc nitrate hexahydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was changed to 0.09 g of ammonium perrhenate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), to obtain a calcined product (powder) of CuNiRe / ZrO2, which is catalyst (A).

[0073] (Comparative Preparation Example 1) <Preparation of Cu / ZrO2 by precipitation method> A 100 mL beaker was charged with 9.5 g of copper nitrate trihydrate (Kanto Chemical Co., Inc.) and dissolved in 49 g of ion-exchanged water to prepare a copper nitrate aqueous solution. Next, a separate 100 mL beaker was charged with 7.5 g of sodium carbonate (Fujifilm Wako Pure Chemical Industries, Ltd.) and dissolved in 42 g of ion-exchanged water to prepare a sodium carbonate aqueous solution. A separate 2 L beaker was charged with 10 g of zirconium oxide (Daiichi Kigenso Kagaku Kogyo Co., Ltd., product name: RC-100 zirconium oxide (white powder, median diameter (d50): 1.5-4 μm)) and 175 g of ion-exchanged water to prepare a zirconium oxide slurry. The copper nitrate aqueous solution was added dropwise to the zirconium oxide slurry over 15 minutes while maintaining the pH at 7 (35°C), and simultaneously the sodium carbonate aqueous solution was added dropwise. After the addition was completed, the solid content of Cu carbonate or hydroxide adhering to the zirconium oxide support was filtered under reduced pressure, and the resulting cake was washed with 1 L of ion-exchanged water. The cake was reslurried, filtered under reduced pressure, and washed with water four times, then dried at 120°C for 18 hours and calcined in air at 500°C for 3 hours to obtain a Cu / ZrO2 calcined product (powder) as a comparative catalyst. The average primary particle size of Cu contained in the obtained fired product was 26 nm.

[0074] (Comparative Preparation Example 2) <Preparation of CuNiRu / ZrO2 by impregnation method> In the preparation of CuNiZn / ZrO2 by the impregnation method of Preparation Example 2, the same procedure as in Preparation Example 2 was carried out, except that 0.27 g of zinc nitrate hexahydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was replaced with 0.12 g of ruthenium chloride (manufactured by N.E. Chemcat Corporation), and a calcined product (powder) of CuNiRu / ZrO2 was obtained as a comparative catalyst.

[0075] (Preparation example B) <Preparation of CuCo / ZrO2 by precipitation method> A 100 mL beaker was charged with 11.2 g of copper nitrate trihydrate (Kanto Chemical Co., Inc.) and 2.7 g of cobalt nitrate hexahydrate (Kanto Chemical Co., Inc.), and 58.1 g of ion-exchanged water was added to dissolve the mixture. This prepared a copper nitrate and cobalt nitrate mixed aqueous solution with a Cu:Co ratio of 5:1 (by mass). Next, a separate 100 mL beaker was charged with 10.7 g of sodium carbonate (Fujifilm Wako Pure Chemical Industries, Ltd.), and 59.1 g of ion-exchanged water was added to dissolve the mixture. A separate 1 L beaker was charged with 10.0 g of zirconium oxide (Daiichi Kigenso Kagaku Kogyo Co., Ltd., product name: RC-100 zirconium oxide (white powder, median diameter (d50): 1.5-4 μm)) and 175.0 g of ion-exchanged water was added to prepare a zirconium oxide slurry. The copper nitrate and cobalt nitrate mixed aqueous solution was added dropwise to the zirconium oxide slurry over 15 minutes while maintaining the pH at 7 (35°C), and simultaneously the sodium carbonate aqueous solution was added dropwise. After the dropwise addition was completed, the solid content of Cu and Co carbonates or hydroxides adhering to the zirconium oxide support was filtered under reduced pressure, and the resulting cake was washed with 1 L of ion-exchanged water. The cake was reslurried, filtered under reduced pressure, and washed three times, and then dried at 120°C for 18 hours to obtain a CuCo / ZrO2 dried product. (Preparation Example 15) <Preparation of CuCoTi / ZrO2 by impregnation method> 2.4 g of titanium tetraisopropoxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was placed in a 100 mL recovery flask, and 23.4 g of 2-propanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added to completely dissolve the titanium tetraisopropoxide. 2.0 g of the dried CuCo / ZrO2 obtained in Preparation Example B was added, and the mixture was concentrated using a rotary evaporator until the liquid was gone. The mixture was then dried at 120°C for 18 hours and calcined in air at 500°C for 3 hours to obtain a calcined CuCoTi / ZrO2 powder, which was used as catalyst (A).

[0076] (Preparation example C) <Preparation of CuMo / ZrO2 by precipitation method> 0.17 g of hexaammonium heptamolybdate tetrahydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was placed in a 50 mL recovery flask, and 6.0 g of ion-exchanged water was added to completely dissolve it. 2.0 g of the calcined Cu / ZrO2 product obtained in Comparative Preparation Example 1 was added, and the mixture was concentrated using a rotary evaporator until the liquid was gone. After that, it was dried at 120°C for 18 hours to obtain a dried CuMo / ZrO2 product. (Preparation Example 16) <Preparation of CuMoTi / ZrO2 by impregnation method> 0.4 g of titanium tetraisopropoxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was placed in a 50 mL recovery flask, and 4.7 g of 2-propanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added to completely dissolve the titanium tetraisopropoxide. 1.9 g of the dried CuMo / ZrO2 obtained in Preparation Example C was then added, and the same procedure as in Preparation Example 15 was repeated to obtain a calcined CuMoTi / ZrO2 powder, which was catalyst (A).

[0077] (Preparation Example 17) <Preparation of CuReTi / ZrO2 by impregnation method> In the preparation of CuMoTi / ZrO2 by the impregnation method of Preparation Example 16, except that 0.17 g of hexaammonium heptamolybdate tetrahydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was changed to 0.1 g of ammonium perrhenate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), the same procedure as in Preparation Example 16 was carried out to obtain a calcined product (powder) of CuReTi / ZrO2, which is catalyst (A).

[0078] (Preparation example D) <Preparation of CuNi / HT by precipitation method> A 100 mL beaker was charged with 10.1 g of copper nitrate trihydrate (Kanto Chemical Co., Inc.) and 2.9 g of nickel nitrate hexahydrate (Kanto Chemical Co., Inc.), and 52.0 g of ion-exchanged water was added to dissolve the mixture. This prepared a mixed aqueous solution of copper nitrate and nickel nitrate with a Cu:Ni ratio of 5:1 (by mass). Next, 9.8 g of sodium carbonate (Fujifilm Wako Pure Chemical Industries Co., Ltd.) was charged to another 100 mL beaker, and 55.0 g of ion-exchanged water was added to dissolve the mixture. A sodium carbonate aqueous solution was prepared. Furthermore, 10.0 g of hydrotalcite (Kyowa Chemical Industry Co., Ltd., product name: Kyoward 500PL) was charged to another 1 L beaker, and 175.0 g of ion-exchanged water was added to prepare a hydrotalcite slurry. The copper nitrate and nickel nitrate mixed aqueous solution was added dropwise to the hydrotalcite slurry over 15 minutes while maintaining the pH at 7 (35°C), and simultaneously the sodium carbonate aqueous solution was added dropwise. After the addition was completed, the same procedure as in Preparation Example B was carried out to obtain a CuNi / HT dried body. (Preparation Example 18) <Preparation of CuNiTi / HT by impregnation method> 0.9 g of titanium tetraisopropoxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was placed in a 100 mL recovery flask, and 11.7 g of 2-propanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added to completely dissolve the titanium tetraisopropoxide. 5.0 g of the dried CuNi / HT obtained in Preparation Example D was then added, and the same procedure as in Preparation Example 15 was repeated to obtain a calcined CuNiTi / HT powder, which was catalyst (A).

[0079] (Preparation example E) <Preparation of CuNi / Al2O3 by precipitation method> A 100 mL beaker was charged with 10.4 g of copper nitrate trihydrate (Kanto Chemical Co., Inc.) and 2.7 g of nickel nitrate hexahydrate (Kanto Chemical Co., Inc.), and 53.9 g of ion-exchanged water was added to dissolve the mixture, preparing a copper nitrate and nickel nitrate mixed aqueous solution with a Cu:Ni ratio of 5:1 (by mass). Next, a separate 100 mL beaker was charged with 10.0 g of sodium carbonate (Fujifilm Wako Pure Chemical Industries, Ltd.), and 55.6 g of ion-exchanged water was added to dissolve the mixture, preparing a sodium carbonate aqueous solution. A separate 1 L beaker was charged with 10.0 g of aluminum oxide (SA6278, Saint-Gobain), and 175.0 g of ion-exchanged water was added to prepare an aluminum oxide slurry. The copper nitrate and nickel nitrate mixed aqueous solution was added dropwise to the aluminum oxide slurry over 15 minutes while maintaining the pH at 7 (35°C), and the sodium carbonate aqueous solution was also added dropwise at the same time. After the addition was completed, the same procedure as in Preparation Example B was repeated to obtain a CuNi / Al2O3 dried body. (Preparation Example 19) <Preparation of CuNiTi / Al2O3 by impregnation method> 2.4 g of titanium tetraisopropoxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was placed in a 100 mL recovery flask, and 31.7 g of 2-propanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added to completely dissolve the titanium tetraisopropoxide. 13.4 g of the dried CuNi / Al2O3 obtained in Preparation Example E was then added, and the same procedure as in Preparation Example 15 was repeated to obtain a calcined CuNiTi / Al2O3 powder, which was catalyst (A).

[0080] (Comparative Preparation Example 3) <Preparation of Cu / HT by precipitation method> A 50 mL beaker was charged with 4.8 g of copper nitrate trihydrate (Kanto Chemical Co., Ltd.) and dissolved in 25.0 g of ion-exchanged water to prepare a copper nitrate aqueous solution. Next, a separate 50 mL beaker was charged with 3.8 g of sodium carbonate (Fujifilm Wako Pure Chemical Industries Co., Ltd.) and dissolved in 21.0 g of ion-exchanged water to prepare a sodium carbonate aqueous solution. A separate 1 L beaker was charged with 5.0 g of hydrotalcite (Kyowa Chemical Industry Co., Ltd., product name: Kyoward 500PL) and dissolved in 87.5 g of ion-exchanged water to prepare a hydrotalcite slurry. The copper nitrate aqueous solution and the sodium carbonate aqueous solution were added dropwise to the hydrotalcite slurry over 15 minutes while maintaining the pH at 7 (35°C). After the addition was completed, the same operation as in Comparative Preparation Example 1 was carried out to obtain a Cu / HT calcined product (powder) as a comparative catalyst.

[0081] (Comparative Preparation Example 4) <Preparation of Cu / Al2O3 by precipitation method> A 100 mL beaker was charged with 9.5 g of copper nitrate trihydrate (Kanto Chemical Co., Inc.) and dissolved in 49.0 g of ion-exchanged water to prepare a copper nitrate aqueous solution. A separate 50 mL beaker was charged with 7.5 g of sodium carbonate (Fujifilm Wako Pure Chemical Industries, Ltd.) and dissolved in 42.0 g of ion-exchanged water to prepare a sodium carbonate aqueous solution. A separate 1 L beaker was charged with 10.0 g of crushed aluminum oxide (SA6278, Saint-Gobain), and 175.0 g of ion-exchanged water was added to prepare an aluminum oxide slurry. The copper nitrate aqueous solution and the sodium carbonate aqueous solution were added dropwise to the aluminum oxide slurry over 15 minutes while maintaining the pH at 7 (35°C). After the addition was completed, the same procedure as in Comparative Preparation Example 1 was repeated to obtain a Cu / Al2O3 calcined product (powder) as a comparative catalyst.

[0082] (Preparation example F) <Preparation of CuNi / ZrO2 by precipitation method> A 100 mL beaker was charged with 14.5 g of copper nitrate trihydrate (Kanto Chemical Co., Inc.) and 3.9 g of nickel nitrate hexahydrate (Kanto Chemical Co., Inc.), and 77.1 g of ion-exchanged water was added to dissolve the mixture. This prepared a copper nitrate and nickel nitrate mixed aqueous solution with a Cu:Ni ratio of 5:1 (by mass). Next, a separate 100 mL beaker was charged with 14.3 g of sodium carbonate (Fujifilm Wako Pure Chemical Industries, Ltd.), and 79.4 g of ion-exchanged water was added to dissolve the mixture. A separate 1 L beaker was charged with 5.0 g of zirconium oxide (Daiichi Kigenso Kagaku Kogyo Co., Ltd., product name: RC-100 zirconium oxide (white powder, median diameter (d50): 1.5-4 μm)) and 87.5 g of ion-exchanged water was added to prepare a zirconium oxide slurry. The copper nitrate and nickel nitrate mixed aqueous solution was added dropwise to the zirconium oxide slurry over 24 minutes while maintaining the pH at 7 (35°C), and the sodium carbonate aqueous solution was also added dropwise at the same time. After the addition was completed, the same procedure as in Preparation Example B was repeated to obtain a CuNi / ZrO2 dried body. (Preparation Example 20) <Preparation of CuNiTi / ZrO2 by impregnation method> 0.6 g of titanium tetraisopropoxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was placed in a 100 mL recovery flask, and 7.7 g of 2-propanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added to completely dissolve the titanium tetraisopropoxide. 12.1 g of the dried CuNi / ZrO2 obtained in Preparation Example F was then added, and the same procedure as in Preparation Example 15 was repeated to obtain a calcined CuNiTi / ZrO2 powder, which was catalyst (A). The average primary particle size of Cu in the obtained fired product was 24 nm.

[0083] (Preparation example G) <Preparation of CuNi / ZrO2 by precipitation method> A 100 mL beaker was charged with 12.9 g of copper nitrate trihydrate (Kanto Chemical Co., Inc.) and 16.8 g of nickel nitrate hexahydrate (Kanto Chemical Co., Inc.), and 66.7 g of ion-exchanged water was added to dissolve the mixture. This prepared a copper nitrate and nickel nitrate mixed aqueous solution with a Cu:Ni ratio of 1:1 (by mass). Next, a separate 200 mL beaker was charged with 21.2 g of sodium carbonate (Fujifilm Wako Pure Chemical Industries, Ltd.), and 117.7 g of ion-exchanged water was added to dissolve the mixture. A separate 1 L beaker was charged with 10.0 g of zirconium oxide (Daiichi Kigenso Kagaku Kogyo Co., Ltd., product name: RC-100 zirconium oxide (white powder, median diameter (d50): 1.5-4 μm)) and 175.0 g of ion-exchanged water was added to prepare a zirconium oxide slurry. The copper nitrate and nickel nitrate mixed aqueous solution was added dropwise to the zirconium oxide slurry over 23 minutes while maintaining the pH at 7 (35°C), and simultaneously the sodium carbonate aqueous solution was added dropwise. After the addition was completed, the same procedure as in Preparation Example B was repeated to obtain a CuNi / ZrO2 dried body. (Preparation Example 21) <Preparation of CuNiTi / ZrO2 by impregnation method> 1.0 g of titanium tetraisopropoxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was placed in a 100 mL recovery flask, and 13.1 g of 2-propanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added to completely dissolve the titanium tetraisopropoxide. 19.2 g of the dried CuNi / ZrO2 obtained in Preparation Example G was then added, and the same procedure as in Preparation Example 15 was repeated to obtain a calcined CuNiTi / ZrO2 powder, which was used as catalyst (A). The average primary particle size of Cu contained in the obtained fired product was 8 nm.

[0084] (Preparation Example 22) <Preparation of CuNiTi / ZrO2 by impregnation method> In preparing CuNiTi / ZrO2 by the impregnation method of Preparation Example 1, the same operations as in Preparation Example 1 were carried out except that the amount of titanium tetraisopropoxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was changed from 0.36 g to 0.3 g, the amount of 2-propanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was changed from 4.7 g to 11.7 g, and the amount of CuNi / ZrO2 calcined product was changed from 2.0 g to 5.0 g, thereby obtaining a CuNiTi / ZrO2 calcined product (powder) as catalyst (A).

[0085] (Preparation Example 23) <Preparation of CuNiTi / ZrO2 by impregnation method> In the preparation of CuNiTi / ZrO2 by the impregnation method of Preparation Example 22, except that the amount of titanium tetraisopropoxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was changed from 0.3 g to 1.2 g, the same procedure as in Preparation Example 22 was carried out to obtain a CuNiTi / ZrO2 calcined product (powder) as catalyst (A).

[0086] (Preparation example H) <Preparation of CuNi / ZrO2 by precipitation method> A 50 mL beaker was charged with 1.3 g of copper nitrate trihydrate (Kanto Chemical Co., Inc.) and 1.6 g of nickel nitrate hexahydrate (Kanto Chemical Co., Inc.), and 6.5 g of ion-exchanged water was added to dissolve the mixture. This prepared a copper nitrate and nickel nitrate mixed aqueous solution with a Cu:Ni ratio of 1:1 (by mass). Next, a separate 50 mL beaker was charged with 2.1 g of sodium carbonate (Fujifilm Wako Pure Chemical Industries, Ltd.), and 11.5 g of ion-exchanged water was added to dissolve the mixture. A separate 1 L beaker was charged with 10.0 g of zirconium oxide (Daiichi Kigenso Kagaku Kogyo Co., Ltd., product name: RC-100 zirconium oxide (white powder, median diameter (d50): 1.5-4 μm)) and 175.0 g of ion-exchanged water was added to prepare a zirconium oxide slurry. The copper nitrate and nickel nitrate mixed aqueous solution was added dropwise to the zirconium oxide slurry over 2 minutes while maintaining the pH at 7 (35°C), and the sodium carbonate aqueous solution was added dropwise at the same time. After the addition was completed, the same operation as in Preparation Example B was carried out to obtain a CuNi / ZrO2 dried body. (Preparation Example 24) <Preparation of CuNiTi / ZrO2 by impregnation method> 0.6 g of titanium tetraisopropoxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was placed in a 50 mL recovery flask, and 8.5 g of 2-propanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added to completely dissolve the titanium tetraisopropoxide. 8.5 g of the dried CuNi / ZrO2 obtained above was then added, and the same procedure as in Preparation Example 15 was repeated to obtain a calcined CuNiTi / ZrO2 powder, which was catalyst (A). The average primary particle size of Cu contained in the obtained fired product was 5 nm.

[0087] (Comparative Preparation Example 5) <Preparation of Cu / ZrO2 by impregnation method> A 100 mL recovery flask was charged with 15.2 g of copper nitrate trihydrate (Kanto Chemical Co., Inc.), and 30.0 g of ion-exchanged water was added to completely dissolve the copper nitrate trihydrate. 10.0 g of zirconium oxide (Daiichi Kigenso Kagaku Kogyo Co., Ltd., product name: RC-100 zirconium oxide (white powder, median diameter (d50): 1.5-4 μm)) was added, and the mixture was concentrated using a rotary evaporator until the liquid was gone. The mixture was then dried at 120 °C for 18 hours and calcined in air at 500 °C for 3 hours to obtain a Cu / ZrO2 calcined product (powder) as a comparative catalyst.

[0088] (Comparative Preparation Example 6) <Preparation of Cu / ZrO2 by precipitation method> A 50 mL beaker was charged with 1.2 g of copper nitrate trihydrate (Kanto Chemical Co., Inc.) and dissolved in 6.0 g of ion-exchanged water to prepare a copper nitrate aqueous solution. Next, a separate 50 mL beaker was charged with 1.0 g of sodium carbonate (Fujifilm Wako Pure Chemical Industries, Ltd.) and dissolved in 5.4 g of ion-exchanged water to prepare a sodium carbonate aqueous solution. A separate 1 L beaker was charged with 10 g of zirconium oxide (Daiichi Kigenso Kagaku Kogyo Co., Ltd., product name: RC-100 zirconium oxide (white powder, median diameter (d50): 1.5-4 μm)) and 175 g of ion-exchanged water to prepare a zirconium oxide slurry. The copper nitrate aqueous solution and the sodium carbonate aqueous solution were added dropwise to the zirconium oxide slurry over 2 minutes while maintaining the pH at 7 (35°C). After the addition was completed, the same procedure as in Comparative Preparation Example 1 was repeated to obtain a Cu / ZrO2 calcined product (powder) as a comparative catalyst. The average primary particle size of Cu contained in the obtained fired product was 5 nm.

[0089] [Examples 1 to 14, Comparative Examples 1 to 4] Study of the third component Example 1 A 1-L five-neck glass flask equipped with a stirrer, thermometer, nitrogen inlet, sampling tube, and a condenser and partial condenser for separating the by-product water was charged with 600.0 g (3.22 mol) of 1-dodecanol (C12) (Kao Corporation, product name: Kalcol 2098) as the raw alcohol, 1.13 g (0.3 mol % based on the raw alcohol) of 48% potassium hydroxide aqueous solution (Kanto Chemical Co., Inc.) as the base catalyst (B), and 0.6 g (0.1 mass % based on the raw alcohol) of the calcined CuNiTi / ZrO2 product prepared in Preparation Example 1 as the catalyst (A). Nitrogen gas was bubbled through the system at a flow rate of 6 L / hr to raise the temperature. When the system temperature reached 240 °C, the nitrogen gas flow rate was changed to 0.13 L / hr, and the reaction was continued for 3 hours. The production conditions and results are shown in Table 1.

[0090] (Examples 2 to 14, Comparative Examples 1 to 4) The reaction was carried out in the same manner as in Example 1, except that the type of catalyst (A) and the reaction time were changed as shown in Table 1. The results are shown in Table 1.

[0091] [Examples 15 to 17, Comparative Examples 1 to 3] Study of the second component The reaction was carried out in the same manner as in Example 1, except that the type of catalyst (A) and the reaction time were changed as shown in Table 2. The results are shown in Table 2.

[0092] [Examples 18 to 20, Comparative Examples 5 to 7] Investigation of raw material alcohol and carrier The reaction was carried out in the same manner as in Example 1, except that the type of raw material alcohol, the type of catalyst (A), and the reaction time were changed as shown in Table 3. The results are shown in Table 3.

[0093] [Examples 21 to 25, Comparative Examples 1, 8 to 9] Investigation of supported amount The reaction was carried out in the same manner as in Example 1, except that the type of catalyst (A) and the reaction time were changed as shown in Table 4. The results are shown in Table 4.

[0094] [Table 1]

[0095] [Table 2]

[0096] [Table 3]

[0097] [Table 4]

[0098] (Summary of results 1: Examination of the third component) In Examples 1 to 14, catalysts (A) were used in which the type of the third component defined in the present application was changed, and comparisons were made with Comparative Examples 1 to 3, which used catalysts that did not contain the second or third component defined in the present application, and Comparative Example 4, which contained Ru, which is not the third component defined in the present application. The results are shown in Table 1. The results in Table 1 reveal the following: In Examples 1 to 11, in which Ti, Zn, Y, Zr, Nb, La, Ce, Sm, Ta, W, or Au was used as the third component, the by-production rate of dimer ester (C24 ester) was lower than in Comparative Example 1, in which the raw material alcohol conversion rate was similar, and it was found that the effect of suppressing the production of by-product ester was excellent. In Examples 12 to 13, in which Fe and Mo were used as the third component, the by-production rate of dimer ester (C24 ester) was lower than in Comparative Example 2, in which the raw material alcohol conversion rate was similar, and it was found that the effect of suppressing the production of by-product ester was excellent. In Example 14, in which Re was used as the third component, the by-production rate of dimer ester (C24 ester) was lower than in Comparative Examples 3 and 4, which had similar raw material alcohol conversion rates, and it was found that this example had an excellent effect of suppressing the production of by-product esters.

[0099] (Summary of Results 2: Examination of the Second Component) In Examples 15 to 17, studies were carried out using catalyst (A) in which the type of second component defined in the present application was changed, and comparisons were made with Comparative Examples 2, 1, and 3 in which catalysts not containing the second and third components defined in the present application were made, and the results are summarized in Table 2. The results in Table 2 reveal the following. In Example 15, in which Co was used as the second component, the by-production rate of dimer ester (C24 ester) was lower than in Comparative Example 2, in which the raw material alcohol conversion rate was similar, and it was found that this example was excellent in suppressing the production of by-product esters. In Example 16, in which Mo was used as the second component, the by-production rate of dimer ester (C24 ester) was lower than in Comparative Example 1, in which the raw material alcohol conversion rate was similar, and it was found that this example was excellent in terms of the effect of suppressing the production of by-product ester. In Example 17, in which Re was used as the second component, the by-production rate of dimer ester (C24 ester) was lower than in Comparative Example 3, in which the raw material alcohol conversion rate was similar, and it was found that this example was excellent in the effect of suppressing the production of by-product ester.

[0100] (Summary of Results 3: Examination of Raw Alcohol and Carrier) In Examples 18 to 20, the raw material alcohol and catalyst (A) were changed and the type of carrier was changed, and the raw material alcohol and carrier corresponding to Examples 18 to 20 were used, but the results were compared with Comparative Examples 5 to 7, which used catalysts that did not contain the second and third components specified in the present application, and the results are summarized in Table 3. The results in Table 3 reveal the following. In Example 18, which used 1-dodecanol (C12) as the raw material alcohol and HT as the carrier, the by-production rate of dimer ester (C24 ester) was lower than in Comparative Example 5, which had a similar raw material alcohol conversion rate, and it was found that Example 18 was excellent in the effect of suppressing the production of by-product ester. In Example 19, which used 1-decanol (C10) as the raw material alcohol and Al2O3 as the carrier, the by-production rate of dimer ester (C20 ester) was lower than in Comparative Example 6, which had a similar raw material alcohol conversion rate, and it was found that Example 19 was excellent in the effect of suppressing the production of by-product ester. In Example 20, which used 1-octadecanol (C18) as the raw material alcohol and ZrO2 as the carrier, the by-production rate of dimer ester (C36 ester) was lower than in Comparative Example 7, which had a similar raw material alcohol conversion rate, and it was found that Example 20 was excellent in the effect of suppressing the production of by-product ester.

[0101] (Summary of Results 4: Examination of Loading Amount) In Examples 21 to 25, studies were carried out using catalyst (A) in which the contents (supported amounts) of the first to third components were changed, and comparisons were made with Comparative Examples 8, 1, and 9 in which catalysts not containing the second and third components specified in the present application were used, and the results are summarized in Table 4. The results in Table 4 reveal the following. In Example 21, which used catalyst (A) in which the mass ratio of the second component to the first component was 0.18 and the mass ratio of the third component to the first component was 0.03, the by-production rate of dimer ester (C24 ester) was lower than in Comparative Example 8, which had a similar raw material alcohol conversion rate, and it was found that this example was excellent in the effect of suppressing the production of by-product ester. In Examples 22 to 24, which used catalyst (A) in which the mass ratio of the second component to the first component was 0.18 to 0.89 and the mass ratio of the third component to the first component was 0.05 to 0.25, the by-production rate of dimer ester (C24 ester) was lower than in Comparative Example 1, in which the raw material alcohol conversion rate was approximately the same, and it was found that these examples were excellent in the effect of suppressing the production of by-product ester. In Example 25, which used catalyst (A) in which the mass ratio of the second component to the first component was 0.67 and the mass ratio of the third component to the first component was 0.40, the by-production rate of dimer ester (C24 ester) was lower than in Comparative Example 9, in which the raw material alcohol conversion rate was similar, and it was found that this example was excellent in the effect of suppressing the production of by-product ester.

Claims

1. A method for producing a Guerbet alcohol, comprising subjecting a raw material alcohol having from 8 to 22 carbon atoms to a Guerbet reaction in the presence of a catalyst (A) containing the following first component, second component, and third component: First component: copper Second component: one selected from the group consisting of cobalt, nickel, molybdenum, and rhenium Third component: at least one selected from the group consisting of titanium, yttrium, zirconium, niobium, cerium, samarium, and tantalum (excluding titanium oxide, zirconium oxide, and cerium oxide, which are the supports of the catalyst (A) described below). the catalyst (A) is a catalyst in which the first component, the second component, and the third component are supported on a carrier, the support of the catalyst (A) is at least one selected from the group consisting of aluminum oxide, activated carbon, titanium oxide, zirconium oxide, zeolite, cerium oxide, and hydrotalcite; A method for producing Guerbet alcohol, wherein the mass ratio of the third component to the first component in the catalyst (A) is 0.001 or more and 0.60 or less.

2. 2. The method for producing Guerbet alcohol according to claim 1, wherein the second component of the catalyst (A) is one selected from the group consisting of cobalt, nickel, and rhenium.

3. The method for producing Guerbet alcohol according to claim 1 or 2, wherein the raw material alcohol is a primary aliphatic alcohol having from 8 to 18 carbon atoms.

4. The method for producing Guerbet alcohol according to any one of claims 1 to 3, wherein a base catalyst (B) is used together with the catalyst (A).

5. 5. The method for producing Guerbet alcohols according to claim 4, wherein the amount of the base catalyst (B) is 0.1 mol % or more and 7 mol % or less based on the total amount of the raw material alcohols.

6. The method for producing Guerbet alcohols according to any one of claims 1 to 5, wherein the amount of the catalyst (A) is 0.01 mass% or more and 10 mass% or less with respect to the total amount of the raw material alcohols in the case of a suspension bed reaction.

7. The method for producing Guerbet alcohol according to any one of claims 1 to 6, wherein the mass ratio of the second component to the first component in the catalyst (A) is 0.10 or more and 9 or less.

8. 8. The method for producing Guerbet alcohol according to claim 7, wherein the mass ratio of the second component to the first component in the catalyst (A) is 0.12 or more and 5 or less.

9. The method for producing Guerbet alcohol according to any one of claims 1 to 7, wherein the mass ratio of the third component to the first component in the catalyst (A) is 0.005 or more and 0.50 or less.

10. The method for producing Guerbet alcohol according to any one of claims 1 to 9, wherein the content of the first component contained in the catalyst (A) is 3% by mass or more and 39% by mass or less.

11. The method for producing Guerbet alcohol according to any one of claims 1 to 10, wherein the content of the second component contained in the catalyst (A) is 1% by mass or more and 20% by mass or less.

12. The method for producing Guerbet alcohol according to any one of claims 1 to 11, wherein the content of the third component contained in the catalyst (A) is 0.1 mass% or more and 10 mass% or less.

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