Classifications

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  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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  • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
  • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
  • B01J21/063—Titanium; Oxides or hydroxides thereof
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  • B01J23/74—Iron group metals
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  • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/847—Vanadium, niobium or tantalum or polonium
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  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/847—Vanadium, niobium or tantalum or polonium
  • B01J23/8474—Niobium
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  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/847—Vanadium, niobium or tantalum or polonium
  • B01J23/8476—Tantalum
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/85—Chromium, molybdenum or tungsten
  • B01J23/88—Molybdenum
  • B01J23/885—Molybdenum and copper
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/85—Chromium, molybdenum or tungsten
  • B01J23/888—Tungsten
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/889—Manganese, technetium or rhenium
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
  • B01J23/8913—Cobalt and noble metals
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
  • B01J23/8926—Copper and noble metals
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/02—Impregnation, coating or precipitation
  • B01J37/0201—Impregnation
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/02—Impregnation, coating or precipitation
  • B01J37/0201—Impregnation
  • B01J37/0209—Impregnation involving a reaction between the support and a fluid
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/02—Impregnation, coating or precipitation
  • B01J37/024—Multiple impregnation or coating
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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  • B01J37/02—Impregnation, coating or precipitation
  • B01J37/03—Precipitation; Co-precipitation
  • B01J37/031—Precipitation
  • B01J37/035—Precipitation on carriers
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
  • C07C29/32—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions without formation of -OH groups
  • C07C29/34—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions without formation of -OH groups by condensation involving hydroxy groups or the mineral ester groups derived therefrom, e.g. Guerbet reaction
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
  • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
  • B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties

Definitions

• the present invention relates to a method for producing gelve alcohol.
• an aliphatic alcohol is reacted in the presence of a base catalyst or a base catalyst and a co-catalyst to remove one molecule of water from two molecules of alcohol, and one molecule of branched dimerized alcohol (Gerve). It is widely known that alcohol) can be obtained, and it is called the Gerve reaction.
• the reaction mechanism of the Gerve reaction consists of the following elementary reactions (1) to (4).
• Patent Document 1 describes alcohol having 3 to 26 carbon atoms as (a) a catalyst composed of an alkaline substance, (b) copper, and a fourth cycle transition metal element (chromium, cobalt, nickel, manganese, iron, zinc). ), And a method for producing a branched dimerized alcohol, which is reacted in the presence of a catalyst which is a group 8 platinum group element (platinum, palladium, ruthenium, rhodium), is disclosed.
• a catalyst which is a group 8 platinum group element (platinum, palladium, ruthenium, rhodium)
• Examples of by-products of the elementary reactions (1) to (4) above include esters having twice the carbon number of the raw material alcohol, that is, the same carbon number as the produced gelve alcohol (hereinafter, also referred to as "by-product ester"). Be done. Since this by-product ester has a boiling point similar to that of the produced gelber alcohol, it is difficult to remove it by distillation, which has been a problem. Therefore, an object of the present invention is to provide a method for producing a high-quality gelber alcohol with few impurities by suppressing the formation of by-product ester.
• the present inventors have found that the above-mentioned problems can be solved by reacting a raw material alcohol having 8 or more and 22 or less 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 a gelber alcohol, in which a raw material alcohol having 8 to 22 carbon atoms is reacted in the presence of a catalyst (A) containing the following first component, second component, and third component.
• 1st component Copper 2nd component: 1 type selected from the group consisting of cobalt, nickel, molybdenum, and rhenium 3rd component: Elements belonging to groups 3 to 10 and 12 of the 4th period of the periodic table, and the first of the periodic table At least one selected from the group consisting of elements belonging to groups 3 to 7 and groups 11 to 12 having a period of 5 to 6 and different from the elements selected as the second component [2] gelve alcohol.
• 1st component Copper 2nd component: 1 type selected from the group consisting of cobalt, nickel, molybdenum, and rhenium 3rd component: Elements belonging to groups 3 to 10 and 12 of the 4th period of the periodic table, and the first of the periodic table At least one element selected from the group consisting of elements belonging to groups 3 to 7 and 11 to 12 having a period of 5 to 6 and different from the element selected as the second component.
• an alcohol having 8 or more and 22 or less carbon atoms (hereinafter, also simply referred to as “raw material alcohol”) is used. From the viewpoint of yield, the raw material alcohol has 8 or more carbon atoms, preferably 9 or more, more preferably 10 or more, and 22 or less, preferably 20 or less, and more preferably 18 or less.
• the raw material alcohol can be used alone or in combination of two or more.
• Examples of the raw material alcohol include primary fatty alcohols and secondary fatty alcohols.
• primary fatty alcohols are preferable from the viewpoint of yield, and among them, the number of carbon atoms is 8 or more and 18 or less.
• a primary aliphatic alcohol is preferable, and a saturated linear primary aliphatic alcohol having 8 or more and 18 or less carbon atoms is more preferable.
• primary fatty alcohols include 1-octanol (C8), 1-nonanol (C9), 1-decanol (C10), 1-undecanol (C11), 1-dodecanol (C12), 1-tridecanol.
• secondary fatty alcohols include 2-octanol (C8), 2-nonanol (C9), 2-decanol (C10), 2-undecanol (C11), 2-dodecanol (C12), and 2-tridecanol.
• Catalyst (A) In the method for producing a gelber alcohol of the present invention, a catalyst (A) containing a specific component is used, but a catalyst (A) in which a specific component is supported on a carrier may be used. By using the catalyst (A), it is possible to obtain a high-quality gelber alcohol that suppresses the formation of by-product esters and has few impurities.
• the catalyst (A) used in the present invention is a catalyst containing the following first component, second component, and third component, and the following first component, second component, and third component are used as carriers. It may be a supported catalyst.
• 1st component Copper 2nd component: 1 type selected from the group consisting of cobalt, nickel, molybdenum, and rhenium 3rd component: Elements belonging to groups 3 to 10 and 12 of the 4th period of the periodic table, and the first of the periodic table At least one element selected from the group consisting of elements belonging to groups 3 to 7 and 11 to 12 having a period of 5 to 6 and different from the element selected as the second component.
• the first component of the catalyst (A) is not particularly limited as long as it is copper (Cu), but may be an oxide.
• the content of the first component (Cu) contained in the catalyst (A) is preferably 0.5% by mass or more, more preferably 1% by mass or more, still more preferably 3% by mass or more, from the viewpoint of yield. From the viewpoint of yield and economic efficiency, it is preferably 45% by mass or less, more preferably 39% by mass or less, and further preferably 36% by mass or less.
• the content of the first component contained in the catalyst (A) can be specifically determined by measurement by the method described in Examples.
• 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, still more preferably 3 nm or more, and preferably. It is 50 nm or less, more preferably 40 nm or less, still more preferably 30 nm or less.
• the average primary particle size of the first component (Cu) contained in the catalyst (A) can be specifically determined by measurement by the method described in Examples.
• 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 is an oxide. You may. Among these second components, one selected from the group consisting of cobalt (Co), nickel (Ni), and rhenium (Re) is preferable from the viewpoint of yield and selectivity.
• 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, still more preferably 2% by mass or more, and yield. From the viewpoint of the rate, it is preferably 30% by mass or less, more preferably 25% by mass or less, and further preferably 20% by mass or less.
• the content of the second component contained in the catalyst (A) can be specifically determined by measurement by the method described in Examples.
• the third component of the catalyst (A) is an element belonging to the 3rd to 10th and 12th groups of the 4th period of the periodic table, and an element belonging to the 3rd to 7th group and the 11th to 12th group of the 5th to 6th period of the periodic table.
• the present invention is not particularly limited as long as it is at least one selected from the group consisting of elements different from the element selected as the second component, but may be an oxide.
• Elements belonging to groups 3-10 and 12 of the 4th period of the periodic table include scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), and cobalt. Examples thereof include (Co), nickel (Ni), and zinc (Zn).
• Elements belonging to groups 3-7 and 11-12 of the 5th period of the periodic table include yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), and silver ( Ag) and cadmium (Cd) can be mentioned.
• Elements belonging to the 3rd to 7th groups and the 11th to 12th groups of the 6th cycle of the periodic table include lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), lutetium (Pm), and samarium (Pm).
• Sm Europium (Eu), Gadrinium (Gd), Terbium (Tb), Dysprosium (Dy), Holmium (Ho), Elbium (Er), Tulum (Tm), Itterbium (Yb), Lutetium (Lu), Hafnium ( Examples include Hf), tantalum (Ta), tungsten (W), lutetium (Re), gold (Au), and mercury (Hg).
• titanium (Ti), iron (Fe), zinc (Zn), yttrium (Y), zirconium (Zr), niobium (Nb), and molybdenum are preferable from the viewpoint of yield and selectivity.
• At least one selected from the group consisting of (Mo), lantern (La), cerium (Ce), yttrium (Sm), tantalum (Ta), tungsten (W), renium (Re), and gold (Au) is preferable. ..
• At least one selected from the group consisting of elements belonging to groups 3 to 7 of the 4th to 6th cycles of the periodic table is preferable from the viewpoint of selectivity and / or yield.
• the elements belonging to the 3rd to 7th periods of the 4th period of the periodic table include scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), and manganese (Mn).
• the elements belonging to the 3rd to 7th periods of the 5th period of the periodic table include yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), and technetium (Tc).
• Elements belonging to the 3rd to 7th cycles of the 6th cycle of the cycle table include lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), and uropyum (Eu). , Gadrinium (Gd), Terbium (Tb), Dysprosium (Dy), Holmium (Ho), Elbium (Er), Turium (Tm), Itterbium (Yb), Lutetium (Lu), Hafnium (Hf), Tantal (Ta) , Tungsten (W), Lutetium (Re).
• titanium (Ti), yttrium (Y), niobium (Nb), lanthanum (La), cerium (Ce), samarium (Sm), and tantalum (Ta) from the viewpoint of yield and selectivity.
• at least one selected from the group consisting of tungsten (W) is preferable.
• 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, still more preferably 0.5, from the viewpoint of yield and selectivity. From the viewpoint of mass% or more and yield, it is preferably 15% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass or less.
• the content of the third component contained in the catalyst (A) can be specifically determined by measurement by the method described in Examples.
• 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, still more preferably 0.04 or more, from the viewpoint of yield. , More preferably 0.05 or more, even more preferably 0.13 or more, even more preferably 0.16 or more, and preferably 10 or less, more preferably 9 or less, still more preferably 6 or less, more. It is even more preferably 5 or less, even more preferably 2 or less, and even more preferably 1 or less.
• 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, still more preferably 0.003 or more, from the viewpoint of yield. , More preferably 0.007 or more, even more preferably 0.01 or more, and preferably 0.8 or less, more preferably 0.7 or less, even more preferably 0.6 or less, even more preferably. It is 0.5 or less.
• 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.
• the carrier of 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 carrier of the 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. ; Etc. can be mentioned.
• the carrier 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 from the viewpoint of versatility and economy.
• the shape of the carrier is not particularly limited, and it is usually a powder, and its median diameter (d50) is usually 1 to 300 ⁇ m, but other shapes derived from the powder may be used if necessary.
• the amount (supported amount) of the first to third components supported on the carrier in 100% by mass of the catalyst (A) is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably, from the viewpoint of yield. Is 5% by mass or more, and from the viewpoint of yield and economy, it is preferably 60% by mass or less, more preferably 50% by mass or less, and further preferably 45% by mass or less.
• “the amount of the first to third components supported on the carrier in 100% by mass of the catalyst (A) (supporting amount)" is the content of the first to third components contained in the catalyst (A). Means total.
• 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, still more preferably 0.15 or more, and From the viewpoint of yield, it is preferably 9 or less, more preferably 5 or less, still more preferably 1 or less.
• 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, still more preferably 0.01 or more, from the viewpoint of yield and selectivity. From the viewpoint of yield, it is preferably 0.60 or less, more preferably 0.50 or less, still more preferably 0.40 or less.
• the shape of the catalyst (A) is not particularly limited, and examples thereof include powders, granules, noodles, and pellets.
• the shapes of granules, noodles, pellets and the like can be produced by granulating and molding the powder catalyst (A) by a known method.
• the median diameter (d50) of the catalyst (A) is preferably 1 ⁇ m or more, more preferably 3 ⁇ m or more, still more preferably 5 ⁇ m or more, still more preferably, from the viewpoint of ease of recovery. Is 7 ⁇ m or more, and from the viewpoint of yield, it is preferably 300 ⁇ m or less, more preferably 200 ⁇ m or less, still more preferably 100 ⁇ m or less, still more preferably 30 ⁇ m or less.
• the median diameter (d50) of the catalyst (A) can be determined by a laser diffraction / scattering type particle size distribution measuring device "LA-920" (manufactured by HORIBA, Ltd.). The measurement is carried out by dispersing 0.05 g in ion-exchanged water as a measurement solvent while stirring (stirring speed: level 4), and calculating the median diameter (d50) using an appropriate relative refractive index.
• the average particle size of the catalyst (A) is preferably 0.2 mm or more, more preferably 0.4 mm or more, still more preferably 0.6 mm or more, from the viewpoint of ease of recovery. And, from the viewpoint of yield, it is preferably 2.0 mm or less, more preferably 1.3 mm or less, still more preferably 0.8 mm or less.
• the average particle size of the catalyst (A) refers to the arithmetic average particle size and can be obtained by calipers. The number of granules for which the average particle size is determined may be 30 randomly selected.
• the average diameter of the catalyst (A) is preferably 1.0 mm or more, more preferably 1.2 mm or more, still more preferably 1.4 mm or more, from the viewpoint of catalyst strength. From the viewpoint of yield, it is preferably 2.5 mm or less, more preferably 2.0 mm or less, still more preferably 1.5 mm or less.
• the average diameter of the catalyst (A) refers to the arithmetic mean diameter and can be obtained by calipers.
• the number of noodles for which the average diameter is determined may be 30 randomly selected.
• 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 the uniformity and yield at the time of filling. From the viewpoint of the above, it is preferably 8 mm or less, more preferably 6 mm or less, still more preferably 4 mm or less.
• the average length of the catalyst (A) refers to the arithmetic mean length and can be obtained by calipers. The number of noodles for which the average length is determined may be 30 randomly selected.
• the average diameter and average height of the catalyst (A) are preferably 1.5 mm or more, more preferably 2.0 mm or more, still more preferably 2. It is 5 mm or more, and from the viewpoint of yield, it is preferably 5.0 mm or less, more preferably 4.0 mm or less, still more preferably 3.0 mm or less.
• the average diameter and the average height of the catalyst (A) refer to the arithmetic mean diameter and the arithmetic mean height, and can be obtained by calipers.
• the number of pellets for which the average diameter or average height is determined may be 30 randomly selected.
• the catalyst (A) used in the present invention can be prepared by a well-known method such as a precipitation method, an impregnation method, an ion exchange method, an alloying method, and an adsorption method.
• a precipitation method such as a precipitation method, an impregnation method, an ion exchange method, an alloying method, and an adsorption method.
• the first component and the second component are supported on the carrier by the precipitation method, and then the third component is supported on the carrier supported by the first component and the second component by the impregnation method.
• the method of causing can be preferably used.
• a precipitation method in which the first component and the second component are supported on a carrier for example, the method shown below can be used.
• the first component-containing water-soluble salt and the second component-containing water-soluble salt are dissolved in ion-exchanged water to prepare a mixed aqueous solution containing the first component and the second component.
• a mixed aqueous solution containing the first component and the second component is prepared.
• an alkaline aqueous solution containing an alkaline component such as sodium carbonate and a slurry containing a carrier component such as zirconium oxide are prepared.
• the mixed aqueous solution containing the first component and the second component is dropped onto the slurry, and at the same time, the alkaline aqueous solution is dropped, and the first component and the second component are carbonates or hydroxides in the slurry.
• the mixture While maintaining a predetermined pH at which it is insolubilized and precipitated, the mixture is added dropwise for a predetermined time to obtain a solid content to which the carbonates or hydroxides of the first and second components are attached to the carrier.
• the solid content is repeatedly filtered and washed, and fired at a predetermined temperature for a predetermined time to obtain a fired product in which the first component and the second component are supported on a carrier.
• an impregnation method for supporting the third component on the carrier on which the first component and the second component are supported for example, the method shown below can be used.
• the third component-containing compound is dissolved in an organic solvent or water, and a calcined product of a solid content in which the first component and the second component are supported on a carrier is added thereto, and the liquid is prepared by reducing the pressure or heating while stirring, for example. After concentrating until it disappears, it is dried at a predetermined temperature and further calcined at a predetermined temperature for a predetermined time to obtain a catalyst (A) which is a calcined product in which the first to third components are supported on a carrier.
• the firing temperature for obtaining the baked product in which the first and second components are supported on the carrier and the baked product in which the first and third components are supported on the carrier is preferably 300 from the viewpoint of the yield of gelbealcohol. ° C. or higher, more preferably 350 ° C. or higher, further preferably 400 ° C. or higher, and preferably 900 ° C. or lower, more preferably 850 ° C. or lower, still more preferably 800 ° C. or lower.
• the firing time for obtaining the baked product in which the first and second components are supported on the carrier and the baked product in which the first and third components are supported on the carrier is preferably 1 from the viewpoint of the yield of gelbealcohol. It is more than an hour, more preferably 2 hours or more, still more preferably 3 hours or more, and preferably 10 hours or less, more preferably 7 hours or less, still more preferably 5 hours or less.
• the firing atmosphere for obtaining a fired product in which the first and second components are supported on a carrier and a fired product in which the first and third components are supported on a carrier is not particularly limited, but for example, an inert product such as nitrogen is used.
• examples thereof include a gas atmosphere, an oxidizing atmosphere such as air, and a reducing atmosphere such as hydrogen.
• an oxidizing atmosphere such as air is preferable from the viewpoint of the yield of gelber alcohol.
• the firing atmosphere may be in a closed state or in a distribution state.
• Base catalyst (B) In the method for producing a gelber alcohol of the present invention, it is preferable to use a base catalyst (B) together with the catalyst (A). By using the base catalyst (B) together with the catalyst (A), it is possible to easily suppress the formation of by-product esters and to easily produce high-quality gelber alcohol with few impurities.
• Examples of the base catalyst (B) include alkali metals or alkaline earth metals, and hydrides, hydroxides, carbonates, bicarbonates, alkoxides and the like thereof.
• Specific examples of alkali metal or alkaline earth metal hydrides, hydroxides, carbonates, hydrogen carbonates, and alkoxide compounds include alkali metal hydroxides such as LiOH, NaOH, KOH, RbOH, and CsOH; Li 2 CO.
• Alkali metal carbonates such as 3 , Na 2 CO 3 , K 2 CO 3 , Rb 2 CO 3 , Cs 2 CO 3 ;
• Alkoxide carbonates such as LiHCO 3 , NaHCO 3 , KHCO 3 , RbHCO 3 , CsHCO 3 ;
• Alkali metal alkoxide compounds such as sodium methoxydo, sodium ethoxide, sodium t-butoxide, potassium methoxydo, potassium ethoxide, potassium t-butoxide; alkaline earth metal water such as Mg (OH) 2 , Ca (OH) 2 Oxides; etc.
• alkali metal hydroxides such as LiOH, NaOH, KOH, RbOH, and CsOH, which are strong bases, from the viewpoint of yield; sodium methoxydo, sodium ethoxyoxide, sodium t-butoxide. , Potassium methoxydo, potassium ethoxydo, potassium t-butoxide and other alkali metal alkoxide compounds are preferable, and among them, NaOH and KOH are more preferable from the viewpoint 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.
• the amount of the base catalyst (B) is preferably 0.05 mol% or more, more preferably 0.1 mol% or more, still more preferably 0.2 mol, based on the total amount of the raw material alcohol from the viewpoint of yield. % Or more, and from the viewpoint of selectivity, it is preferably 7 mol% or less, more preferably 5 mol% or less, still more preferably 3 mol% or less.
• the reaction form of the Gerve reaction is not particularly limited, and it may be a suspension bed reaction or a fixed bed reaction, but it can be appropriately selected depending on the catalytic activity, reaction scale, and the like.
• the material of the reactor used for the Gerve reaction may be stainless steel (SUS201, SUS202, SUS301, SUS302, SUS303, SUS304, SUS305, SUS316, SUS317, SUS329J1, SUS403, SUS405, SUS420, SUS430, SUS430LX, SUS630) or glass.
• the method for producing gelve alcohol of the present invention may be a batch type, a semi-batch type, or a continuous type.
• the reaction type of the reaction is a suspension bed reaction
• a batch type or a semi-batch type is preferable from the viewpoint of operability
• the amount of the catalyst (A) is based on the total amount of the raw material alcohol from the viewpoint of yield. It is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, further preferably 0.1% by mass or more, and from the viewpoint of economic efficiency, preferably 10% by mass or less, more preferably 5 by mass. It is mass% or less, more preferably 1 mass% or less.
• the amount of the catalyst (A) is preferably 10% by mass with respect to the total amount of the raw material alcohol from the viewpoint of yield.
• the above is more preferably 15% by mass or more, further preferably 25% by mass or more, still more preferably 50% by mass or more, and from the viewpoint of economic efficiency, preferably 4000% by mass or less, more preferably 2500% by mass or more.
• it is more preferably 1000% by mass or less, and even more preferably 500% by mass or less.
• the reaction temperature in the Gerve reaction is appropriately determined in consideration of 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, still more preferably 200 ° C. or higher, still more preferably. Is 220 ° C. or higher, and from the viewpoint of selectivity, it is preferably 300 ° C. or lower, more preferably 280 ° C. or lower, still more preferably 260 ° C. or lower.
• the reaction time in the Gerve reaction is appropriately determined depending on the reaction temperature and the type of raw material alcohol, but in the suspension bed reaction, it is usually 1 hour or more from the viewpoint of yield, and from the viewpoint of productivity, it is usually 1 hour or more.
• the LHSV (liquid space velocity) in the fixed bed reaction is preferably 10 / hr or less, more preferably 7 / hr or less, still more preferably 5 / hr or less, still more preferably 3 / hr or less, from the viewpoint of yield. Yes, and from the viewpoint of productivity, it is preferably 0.03 / hr or more, more preferably 0.05 / hr or more, still more preferably 0.1 / hr or more, still more preferably 0.2 / hr or more. is there.
• the pressure of the gas phase at the time of the reaction in the Gerve reaction may be in any state of reduced pressure, normal pressure and pressure, but from the viewpoint of yield and selectivity, it may be reduced pressure and operability. , And from the viewpoint of manufacturing cost, normal pressure may be used.
• the inert gas is not particularly limited, and examples thereof include nitrogen gas, argon gas, carbon dioxide gas, and the like, and among these, nitrogen gas is preferably used.
• the flow of the inert gas can be carried out by a method of flowing above the reaction solution, a method of bubbling in the reaction solution, or the like.
• the flow rate of the inert gas at the time of raising the temperature until reaching the reaction temperature is not particularly limited, but from the viewpoint of yield and selectivity, it is preferably 0.5 L / hr or more, more preferably 3 L, per 1 kg of the reaction solution.
• the flow rate of the inert gas at the time of the reaction reaching the reaction temperature is not particularly limited, but from the viewpoint of yield and selectivity, it is preferably 0.02 L / hr or more, more preferably 0.08 L per 1 kg of the reaction solution.
• the gelber alcohol produced by the production method of the present invention is determined depending on the type of raw material alcohol used, but may be saturated or unsaturated, primary or secondary, or may have a cyclic structure. Further, the number of carbon atoms of the gelber alcohol produced by the production method of the present invention is preferably 16 or more, more preferably 18 or more, still more preferably 20 or more, and preferably 44 or less, from the viewpoint of yield. It is more preferably 40 or less, still more preferably 36 or less.
• the by-product rate of the by-product ester is low and the effect of suppressing the formation of the by-product ester (dimer ester) is excellent, so that the quality is high with few impurities.
• Gerve alcohol can be obtained. Therefore, the gelber alcohol obtained by the production method of the present invention can be used as it is for various purposes, but it can also be purified and used by a distillation operation or the like if necessary.
• Gervealcohol is useful as a raw material or an intermediate raw material for surfactants, fiber oils, fabric softeners, cosmetics, pharmaceuticals, lubricating oils and the like. From the viewpoint of use in these applications, the purity of the gelber alcohol is preferably 95% by mass or more, more preferably 97% by mass or more, still more preferably 98% by mass or more.
• the present invention discloses the following methods for producing gelve alcohol.
• a method for producing a gelber alcohol in which a raw material alcohol having 8 to 22 carbon atoms is reacted in the presence of a catalyst (A) containing the following first component, second component, and third component.
• First component Copper (Cu) 2nd component: 1 type selected from the group consisting of cobalt (Co), nickel (Ni), molybdenum (Mo), and renium (Re) 3rd component: Group 3-10, 12 of the 4th cycle of the periodic table At least selected from the group consisting of the elements to which the elements belong, and the elements belonging to the 3rd to 7th groups and the 11th to 12th groups of the 5th to 6th cycles of the periodic table, which are different from the elements selected as the second component.
• Type 1 ⁇ 2> The method for producing a gelve alcohol according to ⁇ 1>, wherein the raw material alcohol preferably has 9 or more carbon atoms, more preferably 10 or more, and preferably 20 or less, more preferably 18 or less. ..
• ⁇ 3> The method for producing a gelber alcohol according to ⁇ 1> or ⁇ 2>, wherein the raw material alcohol preferably has 8 or more and 20 or less carbon atoms.
• ⁇ 4> The method for producing a gelber alcohol according to ⁇ 1> or ⁇ 2>, wherein the raw material alcohol preferably has 8 or more and 18 or less carbon atoms.
• ⁇ 5> The method for producing a gelber alcohol according to ⁇ 1> or ⁇ 2>, wherein the raw material alcohol preferably has 9 or more and 20 or less carbon atoms.
• ⁇ 6> The method for producing a gelber alcohol according to ⁇ 1> or ⁇ 2>, wherein the raw material alcohol preferably has 9 or more and 18 or less carbon atoms.
• ⁇ 7> The method for producing a gelber alcohol according to ⁇ 1> or ⁇ 2>, wherein the raw material alcohol preferably has 10 or more and 20 or less carbon atoms.
• ⁇ 8> The method for producing a gelve alcohol according to ⁇ 1> or ⁇ 2>, wherein the raw material alcohol preferably has 10 or more and 18 or less carbon atoms.
• ⁇ 9> The method for producing a gelve alcohol according to ⁇ 1> or ⁇ 2>, wherein the raw material alcohol is preferably a primary aliphatic alcohol.
• ⁇ 10> The method for producing a gelve alcohol according to ⁇ 1> or ⁇ 2>, wherein the raw material alcohol is preferably a primary aliphatic alcohol having 8 or more and 18 or less carbon atoms.
• ⁇ 11> The method for producing a gelve alcohol according to ⁇ 1> or ⁇ 2>, wherein the raw material alcohol is preferably a saturated linear primary aliphatic alcohol having 8 or more and 18 or less carbon atoms.
• 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, further preferably 3% by mass or more, and preferably 45.
• 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, further preferably 3 nm or more, and preferably 50 nm or less, more preferably. Is 40 nm or less, more preferably 30 nm or less, according to any one of ⁇ 1> to ⁇ 12>.
• any one of ⁇ 1> to ⁇ 13> which is preferably one selected from the group consisting of cobalt (Co), nickel (Ni), and rhenium (Re). The method for producing gelve alcohol according to the above.
• 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, still more preferably 2% by mass or more, and preferably 30.
• the method for producing gelve alcohol according to any one of.
• ⁇ 17> Among the third components, at least one selected from the group consisting of elements belonging to groups 3 to 7 of the 4th to 6th cycles of the periodic table is preferable, according to any one of ⁇ 1> to ⁇ 15>. How to make gelve alcohol.
• the method for producing gelve alcohol according to ⁇ 17> wherein at least one selected from the group consisting of is preferable.
• 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, still more preferably 0.5% by mass or more, and The method for producing gelve alcohol according to any one of ⁇ 1> to ⁇ 20>, preferably 15% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass or less.
• 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, still more preferably 0.04 or more, and more.
• 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, still more preferably 0.003 or more, and more.
• 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 aluminum oxide, activated carbon, titanium oxide, zirconium oxide, and the like.
• the amount (supporting amount) of the first to third components supported on the carrier is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 5.
• 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, still more preferably 0.15 or more, and preferably 0.15 or more.
• 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, still more preferably 0.01 or more, and preferably.
• the method for producing a gelve alcohol according to any one of ⁇ 1> to ⁇ 26> which is 0.60 or less, more preferably 0.50 or less, still more preferably 0.40 or less.
• the median diameter of the catalyst (A) is preferably 1 ⁇ m or more, more preferably 3 ⁇ m or more, still more preferably 5 ⁇ m or more, still more preferably 7 ⁇ m or more
• the average particle size of the catalyst (A) is preferably 0.2 mm or more, more preferably 0.4 mm or more, still more preferably 0.6 mm or more, and
• the average diameter of the catalyst (A) is preferably 1.0 mm or more, more preferably 1.2 mm or more, still more preferably 1.4 mm or more, and The method for producing a gelber alcohol according to any one of ⁇ 1> to ⁇ 27>, preferably 2.5 mm or less, more preferably 2.0 mm or less, still more preferably 1.5 mm or less.
• 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.
• the method for producing a gelve alcohol according to any one of ⁇ 1> to ⁇ 27> which is more preferably 4 mm or less.
• the average diameter and average height of the catalyst (A) are preferably 1.5 mm or more, more preferably 2.0 mm or more, still more preferably 2.5 mm or more.
• the method for producing a gelve alcohol according to any one of ⁇ 1> to ⁇ 27> which is preferably 5.0 mm or less, more preferably 4.0 mm or less, still more preferably 3.0 mm or less.
• the firing temperature for obtaining the fired product in which the first and second components are supported on the carrier and the fired product in which the first to third components are supported on the carrier is preferably 300 ° C. or higher, more preferably.
• the firing time for obtaining the baked product in which the first and second components are supported on the carrier and the baked product in which the first and third components are supported on the carrier is preferably 1 hour or more, more preferably.
• the gelber alcohol according to any one of ⁇ 24> to ⁇ 33> which is 2 hours or more, more preferably 3 hours or more, preferably 10 hours or less, more preferably 7 hours or less, still more preferably 5 hours or less.
• Manufacturing method. ⁇ 35> The firing atmosphere for obtaining the fired product in which the first and second components are supported on the carrier and the fired product in which the first to third components are supported on the carrier is preferably an oxidizing atmosphere, ⁇ 24> to.
• the method for producing a gelber alcohol according to any one of ⁇ 34> is preferably an oxidizing atmosphere, ⁇ 24> to.
• a base catalyst (B) is used together with the catalyst (A), and the base catalyst (B) is a strong base alkali metal hydroxide such as LiOH, NaOH, KOH, RbOH, CsOH; sodium methoxy.
• Alkali metal alkoxide compounds such as do, sodium ethoxydo, sodium t-butoxide, potassium methoxydo, potassium ethoxydo, and potassium t-butoxide are preferable, and NaOH and KOH are more preferable, any of ⁇ 1> to ⁇ 35>.
• the method for producing gelve alcohol described in Caustic. ⁇ 37> The method for producing a gelber alcohol according to ⁇ 36>, wherein the base catalyst (B) may not be supported on a carrier.
• the amount of the base catalyst (B) is preferably 0.05 mol% or more, more preferably 0.1 mol% or more, still more preferably 0.2 mol% or more, based on the total amount of the raw material alcohol.
• the reaction type of the reaction is a suspension bed reaction, a batch type or a semi-batch type is preferable, and the amount of the catalyst (A) is preferably 0.01% by mass with respect to the total amount of the raw material alcohol.
• the above is more preferably 0.05% by mass or more, further preferably 0.1% by mass or more, and preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 1% by mass or less.
• the reaction type of the reaction is a fixed bed reaction, a continuous type is preferable, and the amount of the catalyst (A) is preferably 10% by mass or more, more preferably 15% by mass, based on the total amount of the raw material alcohol.
• the reaction temperature is preferably 180 ° C. or higher, more preferably 190 ° C. or higher, still more preferably 200 ° C. or higher, still more preferably 220 ° C. or higher, and preferably 300 ° C. or lower, more preferably 280 ° C. or higher.
• the method for producing a gelve alcohol according to any one of ⁇ 1> to ⁇ 40> which is more preferably 260 ° C. or lower.
• the reaction time is preferably 20 hours or less, more preferably 10 hours or less in the suspension bed reaction, and the LHSV (liquid space velocity) in the fixed bed reaction is preferably 10 / hr or less, more preferably. Is 7 / hr or less, more preferably 5 / hr or less, even more preferably 3 / hr or less, and preferably 0.03 / hr or more, more preferably 0.05 / hr or more, still more preferably 0.
• ⁇ 43> The method for producing a gelber alcohol according to any one of ⁇ 1> to ⁇ 42>, wherein the reaction preferably introduces an inert gas into the reaction system and allows the inert gas to flow as a carrier.
• the inert gas is nitrogen gas.
• the flow rate of the inert gas at the time of raising the temperature until reaching the reaction temperature is preferably 0.5 L / hr or more, more preferably 3 L / hr or more, still more preferably 8 L / hr or more per 1 kg of the reaction solution.
• the method for producing a gelve alcohol according to ⁇ 43> or ⁇ 44> which is preferably 30 L / hr or less, more preferably 25 L / hr or less, still more preferably 20 L / hr or less.
• the flow rate of the inert gas at the time of the reaction reaching the reaction temperature is preferably 0.02 L / hr or more, more preferably 0.08 L / hr or more, still more preferably 0.1 L / hr, per 1 kg of the reaction solution.
• the gelve alcohol has a carbon number of preferably 16 or more, more preferably 18 or more, still more preferably 20 or more, and preferably 44 or less, more preferably 40 or less, still more preferably 36 or less. , ⁇ 1> to ⁇ 46>.
• ⁇ 48> The gelve alcohol according to any one of ⁇ 1> to ⁇ 47>, wherein the purity of the gelve alcohol is preferably 95% by mass or more, more preferably 97% by mass or more, still more preferably 98% by mass or more. Manufacturing method.
• ICP emission spectroscopic analysis The quantification of elements contained in the catalysts obtained in the preparation examples and comparative preparation examples was carried out using an ICP emission spectroscopic analyzer (manufactured by Thermo Fisher Scientific Co., Ltd., product name: iCAP6500Duo). , ICP emission spectroscopic analysis (high frequency inductively coupled plasma emission spectroscopic analysis: ICP-AES, ICP-OES).
• the average primary particle size of Cu supported on the carrier contained in the catalysts obtained in the preparation examples and comparative preparation examples is measured by a catalyst analyzer (manufactured by Nippon Bell Co., Ltd.). Product name: BELCAT-B) was used, and the measurement was performed by the pulse method.
• the pretreatment is to reduce CuO at 150 ° C for 4 hours under 5% H 2 / Ar gas flow, and then introduce 5% N 2 O / He gas at 50 ° C until saturation is reached, resulting in total gas consumption.
• the average primary particle size of Cu was measured from.
• Raw material alcohol conversion rate (%) 100- [Amount of remaining raw material alcohol (mol) / Amount of raw material alcohol charged (mol)] x 100
• Dimer ester by-product rate (%) [Amount of produced dimer ester (mol) x 2 / Amount of raw material alcohol charged (mol)] x 100
• 1-dodecanol (C12) is used as the raw material alcohol
• the dimer ester is C24 ester
• the dimer ester is C20 ester or 1-octadecanol (1-octadecanol).
• the dimer ester when C18) is used is C36 ester.
• 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 at the same time, the sodium carbonate aqueous solution was added dropwise.
• the solid content in which Cu and Ni carbonates or hydroxides were attached to the carrier zirconium oxide was filtered under reduced pressure, and the obtained cake was washed with 1 L of ion-exchanged water. After performing the operations of reslurry, vacuum filtration, and washing with water four times, the cake was dried at 120 ° C. for 18 hours and further fired in air at 500 ° C. for 3 hours to obtain a CuNi / ZrO 2 fired product.
• Example 2 Prepared except that 6 g of ion-exchanged water as a solvent was changed to 16 g, and a 28% aqueous ammonia solution (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was added to 16 g of the ion-exchanged water until the pH reached 8. The same operation as in Example 2 was carried out to obtain a CuNiW / ZrO 2 fired product (powder) as the catalyst (A). The average primary particle size of Cu contained in the obtained fired product was 20 nm.
• zirconium oxide manufactured by Daiichi Rare Element Chemical Industry Co., Ltd., product name: RC-100 zirconium oxide (white powder, median diameter (d50): 1.5 to 4 ⁇ m)
• RC-100 zirconium oxide white powder, median diameter (d50): 1.5 to 4 ⁇ m
• 175 g of water was added 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 at the same time, the sodium carbonate aqueous solution was added dropwise.
• the solid content of Cu carbonate or hydroxide attached to the carrier zirconium oxide was filtered under reduced pressure, and the obtained cake was washed with 1 L of ion-exchanged water. After performing the operations of reslurry, vacuum filtration, and washing with water four times, the cake was dried at 120 ° C. for 18 hours and further fired in air at 500 ° C. for 3 hours to obtain Cu / ZrO 2 which is a catalyst for comparative examples. A fired product (powder) was obtained. The average primary particle size of Cu contained in the obtained fired product was 26 nm.
• 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 at the same time, the sodium carbonate aqueous solution was added dropwise.
• the solid content in which Cu and Co carbonates or hydroxides were attached to the carrier zirconium oxide was filtered under reduced pressure, and the obtained cake was washed with 1 L of ion-exchanged water.
• the cake was subjected to three operations of reslurry, vacuum filtration, and washing with water, and then dried at 120 ° C. for 18 hours to obtain a CuCo / ZrO 2 dried product.
• the aqueous solution of copper nitrate and nickel nitrate was added dropwise to the slurry of hydrotalcite over 15 minutes while maintaining the pH at 7 (35 ° C.), and at the same time, the aqueous solution of sodium carbonate was added dropwise. After completion of the dropping, the same operation as in Preparation Example B was carried out to obtain a CuNi / HT dried product.
• 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 at the same time, the sodium carbonate aqueous solution was added dropwise. After completion of the dropping, the same operation as in Preparation Example B was carried out to obtain a CuNi / Al 2 O 3 dried product.
• hydrotalcite manufactured by Kyowa Chemical Industry Co., Ltd., product name: Kyoward 500PL
• a hydrotalcite slurry 87.5 g of ion-exchanged water was added to prepare a hydrotalcite slurry.
• the copper nitrate aqueous solution was added dropwise to the hydrotalcite slurry over 15 minutes while maintaining the pH at 7 (35 ° C.), and at the same time, the sodium carbonate aqueous solution was added dropwise.
• the same operation as in Comparative Preparation Example 1 was carried out to obtain a Cu / HT fired product (powder) as a catalyst for Comparative Example.
• 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 at the same time, the sodium carbonate aqueous solution was added dropwise. After completion of the dropping, the same operation as in Preparation Example B was carried out to obtain a CuNi / ZrO 2 dried product.
• Preparation Example 20 ⁇ Preparation of CuNiTi / ZrO 2 by impregnation method> 0.6 g of titanium tetraisopropoxide (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was placed in a 100 mL eggplant flask, and 7.7 g of 2-propanol (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was added to completely dissolve the mixture. .. After 12.1 g of the CuNi / ZrO 2 dried product obtained in Preparation Example F was added thereto, the same operation as in Preparation Example 15 was carried out to obtain a CuNiTi / ZrO 2 fired product (powder) as the catalyst (A). It was. The average primary particle size of Cu in the obtained fired product was 24 nm.
• 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 at the same time, the sodium carbonate aqueous solution was added dropwise. After completion of the dropping, the same operation as in Preparation Example B was carried out to obtain a CuNi / ZrO 2 dried product.
• 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 at the same time, the sodium carbonate aqueous solution was added dropwise. After completion of the dropping, the same operation as in Preparation Example B was carried out to obtain a CuNi / ZrO 2 dried product.
• zirconium oxide manufactured by Daiichi Rare Element Chemical Industry Co., Ltd., product name: RC-100 zirconium oxide (white powder, median diameter (d50): 1.5 to 4 ⁇ m)
• RC-100 zirconium oxide white powder, median diameter (d50): 1.5 to 4 ⁇ m
• the copper nitrate aqueous solution was added dropwise to the zirconium oxide slurry over 2 minutes while maintaining the pH at 7 (35 ° C.), and at the same time, the sodium carbonate aqueous solution was added dropwise.
• Example 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.
• Examples 15 to 17, Comparative Examples 1 to 3 Examination 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. Was done. The results are shown in Table 2.
• Examples 21 to 25 Comparative Examples 1, 8 to 9
• Examination of supported amount The same as in Example 1 except that the type of catalyst (A) and the reaction time were changed as shown in Table 4. The reaction was carried out. The results are shown in Table 4.
• the dimer ester (C24 ester) by-product rate was low and the effect of suppressing the production of by-product ester was excellent.
• the dimer ester (C24 ester) by-product rate was lower and by-product as compared with Comparative Example 2 in which the raw material alcohol conversion rate was about the same. It was found that the effect of suppressing the formation of ester was excellent.
• the dimer ester (C24 ester) by-product rate was lower than that in Comparative Examples 3 and 4 in which the raw material alcohol conversion rate was about the same, and the by-product ester was used. It was found that the effect of suppressing the formation was excellent.
• Example 16 in which Mo was used as the second component, the dimer ester (C24 ester) by-product rate was lower than that in Comparative Example 1 in which the raw material alcohol conversion rate was about the same, and the by-product ester was produced. It was found to be excellent in suppressing effect.
• Example 17 in which Re was used as the second component the dimer ester (C24 ester) by-product rate was lower than that in Comparative Example 3 in which the raw material alcohol conversion rate was about the same, and the by-product ester was produced. It was found to be excellent in suppressing effect.
• Example 19 in which 1-decanol (C10) was used as the raw material alcohol and Al 2 O 3 was used as the carrier, the dimer ester (C20 ester) sub-dimeric ester (C20 ester) was compared with Comparative Example 6 in which the raw material alcohol conversion rate was similar. It was found that the viability was low and the effect of suppressing the formation of by-product ester was excellent.
• Example 20 in which 1-octadecanol (C18) was used as the raw material alcohol and ZrO 2 was used as the carrier, the dimer ester (C36 ester) sub-dimeric ester (C36 ester) was compared with Comparative Example 7 in which the raw material alcohol conversion rate was similar. It was found that the viability was low and the effect of suppressing the formation of by-product ester was excellent.
• Example 25 using the catalyst (A) in which the mass ratio of the second component to the first component is 0.67 and the mass ratio of the third component to the first component is 0.40, the raw material alcohol conversion rate is about the same. It was found that the dimer ester (C24 ester) by-product ratio was lower than that of Comparative Example 9, and the effect of suppressing the formation of the by-product ester was excellent.

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