Classifications

• • 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
  • B01J29/00—Catalysts comprising molecular sieves
  • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
  • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • B01J29/064—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing iron group metals, noble metals or copper
  • B01J29/072—Iron group metals or copper
• • 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
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
• • 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
  • 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
  • B01J23/72—Copper
• • 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
  • 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
  • B01J23/80—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 zinc, cadmium or mercury
• • 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
  • B01J29/00—Catalysts comprising molecular sieves
  • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
  • B01J29/049—Pillared clays
• • 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
  • B01J37/03—Precipitation; Co-precipitation
  • B01J37/031—Precipitation
  • B01J37/035—Precipitation on carriers
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
  • C07C2523/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of zinc, cadmium or mercury
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
  • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
  • C07C2523/72—Copper

Definitions

• the present invention relates to a method for producing Guerbet alcohol.
• fatty 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 to yield one branched dimerized alcohol (Guerbet alcohol) is widely known and is called the Guerbet reaction.
• the reaction mechanism of the Guerbet reaction is presumed to consist of the following elementary reactions (1) to (4).
• a raw material alcohol having 8 to 36 carbon atoms contains the following first component and second component, and the molar ratio of the first component to the second component (first component/second component) is 2.5. It relates to a method for producing Guerbet alcohol, wherein the reaction is carried out in the presence of a catalyst (A) having a molecular weight of 9 or less.
• First component copper
• Second component an element belonging to groups 3 to 12 of periods 4 to 6 of the periodic table, selected from the group consisting of elements excluding copper and nickel
• the reaction time can be shortened compared to conventional methods, and the yield and selectivity of the produced alcohol can be improved.
• the hydrocarbon compounds that are by-produced separately from the Guerbet alcohol that is produced are difficult to separate during purification such as distillation. It is also required to let
• the present invention provides a method for producing Guerbet alcohol that can shorten the reaction time, improve the yield of Guerbet alcohol to be produced, and reduce the amount of by-products of hydrocarbon compounds.
• the challenge is to
• the present inventors have found that the above problems can be solved by reacting raw material alcohols having 8 to 36 carbon atoms in the presence of a specific catalyst (A). That is, the present invention provides the following [1] and [2].
• a raw material alcohol having 8 to 36 carbon atoms contains the following first component and second component, and the molar ratio of the first component to the second component below (first component/second component) is 2.9
• copper 2nd component an element belonging to Groups 3 to 12 of periods 4 to 6 of the periodic table, which is an element selected from the group consisting of elements excluding copper and nickel [2] Production of Guerbet alcohol A catalyst containing a first component and a second component described below, wherein the molar ratio of the first component to the second component described below (first component/second component) is 2.9 or less.
• First component copper Second component: an element belonging to groups 3 to 12 of periods 4 to 6 of the periodic table, selected from the group consisting of elements excluding copper and nickel
• a method for producing Guerbet alcohol which can shorten the reaction time, improve the yield of Guerbet alcohol to be produced, and reduce the amount of by-products of hydrocarbon compounds. be able to.
• a raw material alcohol having 8 to 36 carbon atoms contains the following first component and second component, and the molar ratio of the first component to the second component below (first component / second).
• the reaction is carried out in the presence of a catalyst (A) having 2 components) of 2.9 or less.
• First component copper
• Second component an element belonging to Groups 3 to 12 of Periods 4 to 6 of the periodic table, one selected from the group consisting of elements excluding copper and nickel
• the reaction It is possible to shorten the time, improve the yield of Guerbet alcohol to be produced, and reduce the amount of by-products of hydrocarbon compounds. Although the reason for this is not clear, it is considered as follows.
• the reaction mechanism of the Guerbet reaction is presumed to consist of the following elementary reactions (1) to (4).
• Allyl Formation of Guerbet Alcohol by Reduction of Alcohol The second component is thought to contribute to atomization of the first component in the process of preparing the catalyst (A).
• the surface area of the atomized first component increases and the surface of the first component is activated, and in the elementary reaction (1) of the reaction mechanism of the Guerbet reaction, the starting alcohol The dehydrogenation reaction is accelerated, and the generated hydrogen is coordinated on the surface of the first component, or the hydrogen coordinated on the surface of the first component moves onto the surface of the second component to form the second component. It is thought that it will be in a coordinated state on the surface. Further, by setting the first component and the second component contained in the catalyst (A) to a specific molar ratio (first component/second component), hydrogen is coordinated in the elementary reaction of (3) above.
• the reduction reaction of the ⁇ , ⁇ -unsaturated aldehyde is promoted on the surface of the second component in the state of Also, it is considered that the reduction reaction of allyl alcohol is promoted on the surface of the second component in which hydrogen is coordinated or on the surface of the first component in which hydrogen is coordinated.
• side reactions such as decarbonylation reaction of ⁇ , ⁇ -unsaturated aldehyde, dehydration reaction and reduction reaction of allyl alcohol proceed, It is believed that hydrocarbon compounds are by-produced.
• the catalyst (A) promotes these elementary reactions to suppress the above-mentioned side reactions, thereby reducing the amount of by-products of hydrocarbon compounds.
• reduction in the amount of by-products of hydrocarbon compounds is also referred to as low selectivity of hydrocarbon compounds.
• played by this invention is not restricted to these ideas.
• Raw material alcohol In the method for producing Guerbet alcohol of the present invention, an alcohol having 8 or more and 36 or less carbon atoms (hereinafter also simply referred to as "raw material alcohol") is used.
• the carbon number of the starting alcohol is 8 or more, preferably 9 or more, more preferably 10 or more, and 36 or less, preferably 22, from the viewpoint of the yield of Guerbet alcohol and low selectivity of hydrocarbon compounds. or less, more preferably 20 or less, still more preferably 18 or less.
• Raw material alcohol can be used individually by 1 type or in combination of 2 or more types.
• Raw material alcohols include primary aliphatic alcohols and secondary aliphatic alcohols.
• primary aliphatic alcohols are preferred from the viewpoint of the yield of Guerbet alcohols and low selectivity of hydrocarbon compounds.
• primary aliphatic alcohols having 8 to 18 carbon atoms are preferred, saturated linear primary aliphatic alcohols having 8 to 18 carbon atoms are more preferable, and saturated linear fatty alcohols having 10 to 16 carbon atoms are more preferable.
• Primary aliphatic alcohols are more preferred, saturated linear primary aliphatic alcohols having 10 to 14 carbon atoms are even more preferred, and saturated linear primary aliphatic alcohols having 10 to 12 carbon atoms are even more preferred. preferable.
• 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), 1 -Saturated linear alcohols such as nonadecanol (C19), 1-eicosanol (C20), 1-heneicosanol (C21), 1-docosanol (C22); cyclohexaneethanol (C8), cyclohexanepropanol (C9), cyclohexanebutanol saturated alicyclic alcohols such as (C10); unsaturated alcohols such as citronellol (C10) and
• secondary aliphatic alcohols include 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), saturated linear alcohols such as 2-docosanol (C22), and the like.
• Catalyst (A) In the method for producing Guerbet alcohol of the present invention, a catalyst (A) containing a specific component in a specific molar ratio is used, but a catalyst (A) in which a specific component is supported on a carrier may also be used. .
• the catalyst (A) By using the catalyst (A), the reaction time can be shortened, the yield of Guerbet alcohol to be produced can be improved, and the by-product amount of hydrocarbon compounds can be reduced.
• the catalyst (A) used in the present invention is a catalyst containing the following first component and second component, and the catalyst (A) in which the following first component and second component are supported on a carrier may be
• First component copper
• Second component an element belonging to groups 3 to 12 of periods 4 to 6 of the periodic table, selected from the group consisting of elements excluding copper and nickel
• 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 4% by mass or more, more preferably 6% by mass or more, from the viewpoint of the yield of Guerbet alcohol and low selectivity to hydrocarbon compounds. , More preferably 7% by mass or more, still more preferably 10% by mass or more, and from the viewpoint of yield and economy of Guerbet alcohol, preferably 55% by mass or less, more preferably 50% by mass or less, and further It is preferably 45% by mass or less, and more preferably 40% by mass.
• 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, from the viewpoint of the yield of Guerbet alcohol and low selectivity for hydrocarbon compounds. , more preferably 3 nm or more, still more preferably 10 nm or more, and preferably 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) is measured by a pulse method using, for example, a catalyst analyzer (manufactured by Nippon Bell Co., Ltd., product name: BELCAT-B). be able to.
• the second component of the catalyst (A) is an element belonging to groups 3 to 12 of periods 4 to 6 of the periodic table, and is not particularly limited as long as it is one selected from the group consisting of elements excluding copper and nickel. may be an oxide. Among these second components, elements belonging to the fourth period of the periodic table are preferable, and zinc (Zn) is more preferable.
• the content of the second component contained in the catalyst (A) is preferably 1% by mass or more, more preferably 3% by mass or more, and still more preferably, from the viewpoint of the yield of Guerbet alcohol and low selectivity to hydrocarbon compounds. is 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, and preferably 80% by mass or less, more preferably 75% by mass or less, and still more preferably 70% by mass or less , more preferably 65% by mass or less, even more preferably 50% by mass or less, even more preferably 45% by mass or less, and even more preferably 40% 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 catalyst (A) may contain a third component other than the first component and the second component as long as the effect of the present invention is not impaired.
• the third component of the catalyst (A) is, for example, an element belonging to Groups 3 to 13 of Periods 2 to 6 of the periodic table, which is at least selected from the group consisting of elements excluding copper, nickel, and the second component. 1 type is mentioned.
• the content of the third component contained in the catalyst (A) is preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 3% by mass or less, even more preferably 1% by mass or less, and even more preferably 1% by mass or less. preferably 0.6% by mass or less, even more preferably 0.3% by mass or less, even more preferably 0.1% by mass or less, even more preferably 0.01% by mass or less, and even more preferably 0% by mass. be.
• the content of the third component contained in the catalyst (A) can be obtained by measurement in the same manner as for the first and second components described above.
• the catalyst (A) is preferably a catalyst in which the first component and the second component are supported on a carrier.
• the carrier of the catalyst (A) is not particularly limited as long as it can support the first component and the second component.
• carriers for the catalyst (A) include carbon materials such as activated carbon, nanocarbon, and carbon black; inorganic materials such as aluminum oxide, iron oxide, copper oxide, titanium oxide, zirconium oxide, zeolite, cerium oxide, and hydrotalcite. ; and the like.
• the carrier of catalyst (A) is preferably at least one selected from the group consisting of zeolite, hydrotalcite, aluminum oxide, activated carbon, titanium oxide, zirconium oxide, and cerium oxide. , aluminum oxide, and hydrotalcite.
• the shape of the carrier is not particularly limited, and it is usually a powder with a median diameter (d50) of usually 1 to 300 ⁇ m.
• the total content of the first component and the second component contained in the catalyst (A) having a carrier is preferably 10% by mass or more from the viewpoint of the yield of Guerbet alcohol and low selectivity for hydrocarbon compounds. , More preferably 20% by mass or more, still more preferably 30% by mass or more, still more preferably 35% by mass or more, still more preferably 40% by mass or more, still more preferably 50% by mass or more, still more preferably 55% by mass % or more, more preferably 60 mass % or more, and preferably 90 mass % or less, more preferably 85 mass % or less, still more preferably 80 mass % or less, and even more preferably 75 mass % or less.
• Catalyst (A) may comprise the first component and the second component without a support.
• the total content of the first component and the second component contained in the catalyst (A) that does not have a support is preferably 50% by mass from the viewpoint of the yield of Guerbet alcohol and low selectivity for hydrocarbon compounds. Above, more preferably 60% by mass or more, still more preferably 65% by mass or more, and even more preferably 70% by mass or more.
• the total content of the first component and the second component contained in the catalyst (A) is, from the viewpoint of the yield of Guerbet alcohol and low selectivity of hydrocarbon compounds, when the first component is 10% by mass or more , preferably 45% by mass or more, more preferably 50% by mass or more, still more preferably 60% by mass or more, and preferably 90% by mass or less, more preferably 85% by mass or less, further preferably 80% by mass or less is.
• the total content of the first component and the second component contained in the catalyst (A) is preferably 30% by mass or more, more preferably 40% by mass when the first component is less than 10% by mass. % by mass or more, more preferably 50% by mass or more, and preferably 80% by mass or less, more preferably 75% by mass or less.
• the total abundance of the first component and the second component contained in the catalyst (A) is less than the amount of the first component contained in the catalyst (A).
• the abundance is 0.3 mol parts or more with respect to 10000 mol parts of raw material alcohol, it is preferably 1.2 mol parts or more, more preferably 1.5 mol parts or more with respect to 10000 mol parts of raw material alcohol.
• Yes preferably 2.4 parts by mole or less, more preferably 2.2 parts by mole or less, still more preferably 2 mole parts or less.
• the total amount of the first component and the second component contained in the catalyst (A) is 0 relative to 10000 mol parts of the raw alcohol.
• it is preferably 0.8 mol parts or more, more preferably 1.0 mol parts or more, and preferably 1.8 mol parts or less with respect to 10000 mol parts of the raw material alcohol. , more preferably 1.5 mol parts or less.
• the molar ratio of the first component to the second component in the catalyst (A) is 2.9 or less from the viewpoint of the yield of Guerbet alcohol and low selectivity for hydrocarbon compounds, preferably 2.7 or less, more preferably 2.5 or less, still more preferably 2.3 or less, and preferably 0.01 or more, more preferably 0.05 or more, still more preferably 0.11 Above, more preferably 0.4 or more, still more preferably 0.6 or more, and still more preferably 0.8 or more.
• the molar ratio of the third component to the sum of the first and second components in catalyst (A) is preferably less than 0.004, more preferably less than 0.004. 003, more preferably less than 0.002, even more preferably less than 0.001, and even more preferably less than 0.0001.
• the shape of the catalyst (A) is not particularly limited, and examples thereof include powder, granules, noodles, and pellets.
• the shapes such as granules, noodles, and pellets 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, and even more preferably, from the viewpoint of ease of recovery. is 7 ⁇ m or more, and is preferably 300 ⁇ m or less, more preferably 200 ⁇ m or less, even more preferably 100 ⁇ m or less, and even more preferably 30 ⁇ m or less from the viewpoint of the yield of Guerbet alcohol and low selectivity of hydrocarbon compounds. .
• the median diameter (d50) of the catalyst (A) can be determined by a laser diffraction/scattering particle size distribution analyzer "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, and still 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 still more preferably 0.8 mm or less from the viewpoint of the yield of Guerbet alcohol and low selectivity of hydrocarbon compounds.
• the average particle size of the catalyst (A) refers to the arithmetic average particle size, and can be obtained with a vernier caliper.
• the number of granules for which the average particle size is determined may be 30 randomly selected granules.
• the average diameter of the catalyst (A) is preferably 1.0 mm or more, more preferably 1.2 mm or more, and still more preferably 1.4 mm or more, from the viewpoint of catalyst strength. , and from the viewpoint of the yield of Guerbet alcohol and low selectivity of hydrocarbon compounds, it is preferably 2.5 mm or less, more preferably 2.0 mm or less, and even more preferably 1.5 mm or less.
• the average diameter of catalyst (A) refers to the arithmetic mean diameter, which can be determined with a vernier caliper. 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 a low selectivity to hydrocarbon compounds, it is preferably 8 mm or less, more preferably 6 mm or less, and even more preferably 4 mm or less.
• the average length of the catalyst (A) refers to the arithmetic average length, which can be determined with a vernier caliper. 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, and still more preferably 2.0 mm or more, from the viewpoint of catalyst strength. It is 5 mm or more, and from the viewpoint of the yield of Guerbet alcohol and low selectivity to hydrocarbon compounds, it is preferably 5.0 mm or less, more preferably 4.0 mm or less, and even more preferably 3.0 mm or less.
• the average diameter and average height of the catalyst (A) refer to the arithmetic average diameter and arithmetic average height, which can be obtained with vernier calipers.
• the number of pellets for which the average diameter or average height is determined may be 30 randomly selected pellets.
• the catalyst (A) used in the present invention can be prepared by known methods such as precipitation, impregnation, ion exchange, alloying, and adsorption.
• a method of supporting the first component and the second component on a carrier by a precipitation method can be suitably used.
• a precipitation method for supporting the first component and the second component on the carrier for example, the following method can be used.
• 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 an aqueous solution containing the first component and the second component.
• an alkaline aqueous solution containing an alkaline component such as sodium carbonate and a slurry containing a carrier component such as zeolite are prepared.
• the aqueous solution containing the first component and the second component is added dropwise to the slurry, and at the same time, the alkaline aqueous solution is added dropwise to insolubilize the first component and the second component as carbonates or hydroxides in the slurry. It is dropped for a predetermined period of time while maintaining a predetermined pH for precipitation to obtain a solid content in which the carbonates or hydroxides of the first component and the second component adhere to the carrier. This solid content is repeatedly filtered and washed, and then 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 the carrier.
• the firing temperature for obtaining the fired product in which the first and second components are supported on the carrier is preferably 300° C. or higher, more preferably 350° C., from the viewpoint of the yield of Guerbet alcohol and low selectivity of hydrocarbon compounds. Above, more preferably 400° C. or higher, preferably 900° C. or lower, more preferably 850° C. or lower, still more preferably 800° C. or lower.
• the firing time for obtaining the fired product in which the first and second components are supported on the carrier is preferably 1 hour or more, more preferably 2 hours, from the viewpoint of the yield of Guerbet alcohol and low selectivity of hydrocarbon compounds. Above, more preferably 3 hours or more, preferably 10 hours or less, more preferably 7 hours or less, still more preferably 5 hours or less.
• the firing atmosphere for obtaining the fired product in which the first and second components are supported on the carrier is not particularly limited, but examples 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 preferable from the viewpoint of yield of Guerbet alcohol and low selectivity to hydrocarbon compounds.
• the firing atmosphere may be in a closed state or in a flowing state.
• 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 base catalyst (B) together with the catalyst (A), the reaction time can be shortened, the yield of the Guerbet alcohol produced can be improved, and the amount of by-production of hydrocarbon compounds can be easily reduced. can.
• Examples of the base catalyst (B) include alkali metals or alkaline earth metals, and their hydrides, hydroxides, carbonates, hydrogencarbonates, alkoxides, and the like.
• alkali metal or alkaline earth metal hydrides, hydroxides, carbonates, hydrogencarbonates, and alkoxide compounds include alkali metal hydroxides such as LiOH, NaOH, KOH, RbOH, and CsOH; Alkali metal carbonates such as 3 , Na2CO3 , K2CO3 , Rb2CO3 , Cs2CO3 ; Alkali metal hydrogencarbonates such as LiHCO3 , NaHCO3 , KHCO3 , RbHCO3 , CsHCO3 ; alkali metal alkoxide compounds such as sodium methoxide, sodium ethoxide, sodium t-butoxide, potassium methoxide, potassium ethoxide, potassium t-butoxide; alkaline earth metal water such as Mg(OH)
• alkali metal hydroxides such as LiOH, NaOH, KOH, RbOH and CsOH, which are strong bases, from the viewpoint of yield of Guerbet alcohol and low selectivity of hydrocarbon compounds; sodium Alkali metal alkoxide compounds such as methoxide, sodium ethoxide, sodium t-butoxide, potassium methoxide, potassium ethoxide, and potassium t-butoxide are preferred, and among them, NaOH and KOH are more preferred from the viewpoint of versatility and economy. , KOH are more preferred.
• the basic catalyst (B) can be used alone or in combination of two or more.
• the basic catalyst (B) may be one that is not supported on a carrier.
• the amount of the basic catalyst (B) is preferably 0.1 mol part or more, more preferably 0.1 mol part or more, based on 100 mol parts of the total amount of raw material alcohols, from the viewpoint of the yield of Guerbet alcohol and low selectivity of hydrocarbon compounds. 0.2 mol parts or more, more preferably 0.3 mol parts or more, and from the viewpoint of selectivity, preferably 7 mol parts or less, more preferably 5 mol parts or less, still more preferably 3 mol parts or less.
• a raw material alcohol having 8 to 36 carbon atoms is reacted in the presence of a catalyst (A) in which a specific component is supported on a carrier (dehydration condensation reaction (Guerbet reaction)). to produce Guerbet alcohol.
• the catalyst (A) may be one that is not supported on a carrier.
• the form of use of the catalyst (A) for the Guerbet reaction is not particularly limited, and may be either a suspended bed reaction or a fixed bed reaction, and can be appropriately selected according to the catalytic activity, reaction scale, and the like.
• the material of the reactor used for 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.
• the reaction mode of 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.
• the reaction is a suspended bed reaction, a batch system or a semi-batch system is preferable from the viewpoint of operability, and the amount of the catalyst (A) is It is preferably 0.001 parts by mass or more, more preferably 0.005 parts by mass or more, and still more preferably 0.01 parts by mass or more with respect to 100 parts by mass of the total amount of alcohol, and from the viewpoint of economy, It is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and even more preferably 1 part by mass or less.
• the reaction is a fixed bed reaction
• a continuous system is preferred from the viewpoint of the yield of Guerbet alcohol and the selectivity of hydrocarbon compounds.
• it is preferably 10 parts by mass or more, more preferably 15 parts by mass or more, still more preferably 25 parts by mass or more, and even more preferably 50 parts by mass or more with respect to 100 parts by mass of the total amount of raw material alcohols.
• it is preferably 4000 parts by mass or less, more preferably 2500 parts by mass or less, even more preferably 1000 parts by mass or less, and even more preferably 500 parts by mass or less.
• the reaction temperature in the Guerbet reaction is appropriately determined in consideration of the boiling point of the raw material alcohol, but from the viewpoint of the yield of Guerbet alcohol and low selectivity of hydrocarbon compounds, it is preferably 180 ° C. or higher, more preferably 190 ° C. or higher. , more preferably 200° C. or higher, still 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 still more preferably 260° C. or lower.
• the reaction time in the Guerbet reaction is appropriately determined according to the reaction temperature and the type of raw material alcohol.
• the LHSV liquid hourly space velocity
• the LHSV liquid hourly space velocity
• the pressure of the gas phase during the reaction in the Guerbet reaction may be any of reduced pressure, normal pressure, and increased pressure. or normal pressure from the viewpoint of operability and economy.
• an inert gas into the reaction system and circulate the inert gas as a carrier, from the viewpoint of the yield of Guerbet alcohol and low selectivity of hydrocarbon compounds.
• the inert gas include, but are not limited to, nitrogen gas, argon gas, etc. Among these, nitrogen gas is preferably used.
• the inert gas can be circulated by a method of circulating above the reaction liquid, a method of bubbling in the reaction liquid, or the like.
• the flow rate of the inert gas during heating until the reaction temperature is reached is not particularly limited, but from the viewpoint of the yield of Guerbet alcohol and low selectivity for hydrocarbon compounds, it is preferably 0.5 L per 1 kg of the reaction liquid.
• the flow rate of the inert gas during the reaction when the reaction temperature is reached is not particularly limited, but from the viewpoint of the yield of Guerbet alcohol and the low selectivity of hydrocarbon compounds, it is preferably 0.02 L/hr per 1 kg of the reaction solution.
• L/hr or more preferably 0.08 L/hr or more, still more preferably 0.1 L/hr or more, and from the viewpoint of economy, preferably 10 L/hr or less, more preferably 5 L/hr or less, still more preferably 2 L/hr or less.
• the Guerbet alcohol produced by the production method of the present invention may be saturated or unsaturated, primary or secondary, and may have a cyclic structure, depending on the type of raw material alcohol used.
• 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, and still more preferably 20, from the viewpoint of the yield of Guerbet alcohol and low selectivity of hydrocarbon compounds. and is preferably 72 or less, more preferably 44 or less, even more preferably 40 or less, and even more preferably 36 or less.
• the reaction time can be shortened, the yield of Guerbet alcohol produced can be improved, and the amount of hydrocarbon by-products can be reduced.
• the Guerbet alcohol obtained by the production method of the present invention can be used for various purposes as it is, but can also be used after being purified by distillation or the like, if necessary. Guerbet alcohols are useful as raw materials or intermediate raw materials for surfactants, textile oils, softeners, cosmetics, pharmaceuticals, lubricating oils, and the like. From the viewpoint of use in these applications, the purity of Guerbet alcohol is preferably 95% by mass or more, more preferably 97% by mass or more, and still more preferably 98% by mass or more.
• the present invention discloses the following method for producing Guerbet alcohol.
• a raw material alcohol having 8 to 36 carbon atoms contains the following first component and second component, and the molar ratio of the first component to the second component below (first component/second component) is 2.9 or less
• 1st component copper 2nd component: an element belonging to groups 3 to 12 of periods 4 to 6 of the periodic table, selected from the group consisting of elements excluding copper and nickel ⁇ 2>
• Production of Guerbet alcohol according to ⁇ 1> wherein the molar ratio of the first component to the second component (first component/second component) in the catalyst (A) is preferably 0.01 or more and 2.9 or less.
• ⁇ 4> Any one of ⁇ 1> to ⁇ 3>, wherein the molar ratio of the first component to the second component (first component/second component) in the catalyst (A) is preferably 0.11 or more and 2.5 or less
• the method for producing Guerbet alcohol according to . ⁇ 5> the molar ratio of the first component to the second component (first component/second component) in the catalyst (A) is preferably 0.4 or more, more preferably 0.6 or more, and still more preferably 0.8 or more;
• the method for producing Guerbet alcohol according to any one of ⁇ 1> to ⁇ 4> which is preferably 2.3 or less.
• ⁇ 6> The method for producing Guerbet alcohol according to any one of ⁇ 1> to ⁇ 5>, wherein the content of the first component contained in the catalyst (A) is preferably 4% by mass or more and 55% by mass or less.
• ⁇ 7> The method for producing Guerbet alcohol according to any one of ⁇ 1> to ⁇ 6>, wherein the content of the first component contained in the catalyst (A) is preferably 6% by mass or more and 50% by mass or less.
• ⁇ 8> The method for producing Guerbet alcohol according to any one of ⁇ 1> to ⁇ 7>, wherein the content of the first component contained in the catalyst (A) is preferably 7% by mass or more and 45% by mass or less.
• ⁇ 9> The method for producing Guerbet alcohol according to any one of ⁇ 1> to ⁇ 8>, wherein the content of the first component contained in the catalyst (A) is preferably 10% by mass or more and 40% by mass or less.
• ⁇ 11> The method for producing Guerbet alcohol according to any one of ⁇ 1> to ⁇ 10>, wherein the average primary particle size of the first component contained in the catalyst (A) is preferably 1 nm or more and 40 nm or less.
• ⁇ 12> The method for producing Guerbet alcohol according to any one of ⁇ 1> to ⁇ 11>, wherein the average primary particle size of the first component contained in the catalyst (A) is preferably 3 nm or more and 30 nm or less.
• ⁇ 13> The method for producing Guerbet alcohol according to any one of ⁇ 1> to ⁇ 12>, wherein the content of the second component contained in the catalyst (A) is preferably 3% by mass or more and 75% by mass or less.
• ⁇ 14> The method for producing Guerbet alcohol according to any one of ⁇ 1> to ⁇ 13>, wherein the content of the second component contained in the catalyst (A) is preferably 5% by mass or more and 70% by mass or less.
• ⁇ 15> The method for producing Guerbet alcohol according to any one of ⁇ 1> to ⁇ 14>, wherein the content of the second component contained in the catalyst (A) is preferably 10% by mass or more and 65% by mass or less.
• ⁇ 16> The method for producing Guerbet alcohol according to any one of ⁇ 1> to ⁇ 15>, wherein the content of the second component contained in the catalyst (A) is preferably 15% by mass or more and 50% by mass or less.
• ⁇ 17> The method for producing Guerbet alcohol according to any one of ⁇ 1> to ⁇ 15>, wherein the content of the second component contained in the catalyst (A) is preferably 15% by mass or more and 45% by mass or less.
• ⁇ 18> The method for producing Guerbet alcohol according to any one of ⁇ 1> to ⁇ 15>, wherein the content of the second component contained in the catalyst (A) is preferably 15% by mass or more and 40% by mass or less.
• the catalyst (A) is preferably a catalyst in which the first component and the second component are supported on a carrier.
• the carrier of the catalyst (A) is preferably at least one selected from the group consisting of zeolite, aluminum oxide, and hydrotalcite.
• ⁇ 24> Any one of ⁇ 19> to ⁇ 23>, wherein the total content of the first component and the second component contained in the catalyst (A) having the carrier is preferably 35% by mass or more and 75% by mass or less.
• method for producing Guerbet alcohol ⁇ 27> ⁇ 19> to ⁇ 23>, wherein the total content of the first component and the second component contained in the catalyst (A) having the carrier is preferably 55% by mass or more and 75% by mass or less.
• method for producing Guerbet alcohol ⁇ 28> ⁇ 19> to ⁇ 23>, wherein the total content of the first component and the second component contained in the catalyst (A) having the carrier is preferably 60% by mass or more and 75% by mass or less.
• the content of the third component contained in the catalyst (A) is preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 3% by mass or less, even more preferably 1% by mass or less, and more More preferably 0.6% by mass or less, still more preferably 0.3% by mass or less, still more preferably 0.1% by mass or less, still more preferably 0.01% by mass or less, still more preferably 0% by mass
• the molar ratio of the third component to the sum of the first and second components in catalyst (A) (third component/total of first and second components) is preferably less than 0.004, more preferably less than 0.004.
• the first component contained in the catalyst (A) is 10% by mass or more, and the total content of the first component and the second component contained in the catalyst (A) is preferably 45% by mass or more, and more Preferably 50% by mass or more, more preferably 60% by mass or more, and preferably 90% by mass or less, more preferably 85% by mass or less, still more preferably 80% by mass or less, ⁇ 1> to ⁇ 30 >
• the first component contained in the catalyst (A) is less than 10% by mass, and the total content of the first component and the second component contained in the catalyst (A) is preferably 30% by mass or more, or more Production of Guerbet alcohol according to ⁇ 1> to ⁇ 31>, which is preferably 40% by mass or more, more preferably 50% by mass or more, and preferably 80% by mass or less, more preferably 75% by mass or less Method.
• the amount of the first component contained in the catalyst (A) is 0.3 mol parts or more with respect to 10000 mol parts of the raw material alcohol, and the first component and the second component contained in the catalyst (A)
• the total amount is preferably 1.2 mol parts or more, more preferably 1.5 mol parts or more, and preferably 2.4 mol parts or less, more preferably 2 .2 mol parts or less, more preferably 2 mol parts or less, the method for producing Guerbet alcohol according to ⁇ 1> to ⁇ 32>.
• the amount of the first component contained in the catalyst (A) is less than 0.3 mol parts per 10000 mol parts of the raw material alcohol, and the first component and the second component contained in the catalyst (A) The total amount is preferably 0.8 mol parts or more, more preferably 1.0 mol parts or more, and preferably 1.8 mol parts or less, more preferably 1
• ⁇ 35> The method for producing Guerbet alcohol according to any one of ⁇ 1> to ⁇ 34>, wherein preferably a base catalyst (B) is used together with the catalyst (A).
• ⁇ 36> The method for producing Guerbet alcohol according to ⁇ 35>, wherein the basic catalyst (B) is preferably NaOH or KOH.
• the amount of the basic catalyst (B) is preferably 0.2 mol parts or more and 5 mol parts or less per 100 mol parts of the total amount of raw material alcohols.
• ⁇ 39> The method for producing Guerbet alcohol according to any one of ⁇ 1> to ⁇ 38>, wherein the raw material alcohol is preferably a saturated linear primary aliphatic alcohol having 8 to 18 carbon atoms.
• the raw material alcohol is preferably a saturated linear primary aliphatic alcohol having 10 to 16 carbon atoms.
• ⁇ 41> The method for producing Guerbet alcohol according to any one of ⁇ 1> to ⁇ 39>, wherein the raw material alcohol is preferably a saturated linear primary aliphatic alcohol having 10 to 14 carbon atoms.
• ⁇ 42> The method for producing Guerbet alcohol according to any one of ⁇ 1> to ⁇ 39>, wherein the raw material alcohol is preferably a saturated linear primary aliphatic alcohol having 10 or more and 12 or less carbon atoms.
• ⁇ 43> The method for producing Guerbet alcohol according to any one of ⁇ 1> to ⁇ 42>, wherein the number of carbon atoms in the Guerbet alcohol is preferably 16 or more and 44 or less.
• ⁇ 44> The method for producing Guerbet alcohol according to any one of ⁇ 1> to ⁇ 43>, wherein the number of carbon atoms in the Guerbet alcohol is preferably 18 or more and 40 or less.
• ⁇ 45> The method for producing Guerbet alcohol according to any one of ⁇ 1> to ⁇ 44>, wherein the number of carbon atoms in the Guerbet alcohol is preferably 20 or more and 36 or less.
• the first component (Cu), the second component, and the third component contained in the catalyst were quantified using an ICP emission spectrometer (manufactured by Thermo Fisher Scientific, product name: iCAP6500Duo) was used to perform ICP emission spectrometry (high frequency inductively coupled plasma emission spectrometry: ICP-AES, ICP-OES).
• C19 alkane and C20 alkane represent alkane having 19 carbon atoms and alkane having 20 carbon atoms, respectively.
• the resulting Guerbet alcohol is C24 Guerbet alcohol
• the by-product hydrocarbon compounds are C23 alkane and C24 alkane.
• C23 alkane and C24 alkane represent alkane having 23 carbon atoms and alkane having 24 carbon atoms, respectively.
• the resulting Guerbet alcohol is C32 Guerbet alcohol
• the by-product hydrocarbon compounds are C31 alkane and C32 alkane.
• C31 alkane and C32 alkane represent alkane having 31 carbon atoms and alkane having 32 carbon atoms, respectively.
• a precipitate (a solid content in which carbonates or hydroxides of Cu and Zn adhere to synthetic zeolite as a carrier) was filtered under reduced pressure, and the obtained cake was washed with 400 mL of ion-exchanged water. The cake was reslurried, filtered under reduced pressure, and washed with water four times, dried at 120° C. for 16 hours, and further calcined in air at 500° C. for 3 hours to obtain a Cu—Zn/zeolite calcined product (powder) ( Catalyst a1) was obtained.
• the content of Cu and Zn contained in the obtained Cu—Zn/zeolite fired product was determined by ICP emission spectrometry, the content of Cu was 34.2% by mass and the content of Zn was 11.8% by mass. %Met.
• Preparation Example 1 ⁇ Preparation of Cu—Zn/zeolite by precipitation method> 15 g of copper nitrate trihydrate (manufactured by Kanto Chemical Co., Ltd.) and 9 g of zinc nitrate hexahydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) are placed in a 250 mL beaker, and 78 g of ion-exchanged water is added to dissolve. A metal salt aqueous solution was prepared.
• Preparation Example 2 ⁇ Preparation of Cu—Zn/zeolite by precipitation method> 15 g of copper nitrate trihydrate (manufactured by Kanto Chemical Co., Ltd.) and 18 g of zinc nitrate hexahydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) are placed in a 250 mL beaker, and 78 g of deionized water is added to dissolve. A metal salt aqueous solution was prepared.
• Comparative Preparation Example 1 except that the aqueous metal salt solution was added dropwise to the ion-exchanged water to which the synthetic zeolite was not added over 39 minutes while maintaining the pH at 7 (20° C.), and at the same time the aqueous sodium carbonate solution was added dropwise.
• a Cu—Zn sintered product (powder) (catalyst A6) was obtained by performing the same operation.
• the content of Cu and Zn contained in the obtained Cu—Zn fired product was determined by ICP emission spectrometry, the content of Cu was 37.0% by mass and the content of Zn was 38.3% by mass. there were.
• Preparation Example 7 ⁇ Preparation of Cu—Zn/HT by precipitation method> The same operation as in Preparation Example 2 was performed except that hydrotalcite (manufactured by Kyowa Chemical Industry Co., Ltd., product name: Kyoward 500PL) was used instead of synthetic zeolite (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.). A Zn/HT fired product (powder) (catalyst A7) was obtained. When the content of Cu and Zn contained in the obtained Cu—Zn/HT fired product was determined by ICP emission spectrometry, the content of Cu was 33.7% by mass and the content of Zn was 38.5% by mass. %Met.
• Preparation Example 8 ⁇ Preparation of Cu—Zn/Al 2 O 3 by precipitation method> The same operation as in Preparation Example 2 was performed except that aluminum oxide (manufactured by Mizusawa Chemical Industry Co., Ltd., product name: GP-20) was used instead of synthetic zeolite (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.). / Al 2 O 3 calcined product (powder) (catalyst A8) was obtained. When the content of Cu and Zn contained in the obtained Cu—Zn/Al 2 O 3 baked product was determined by ICP emission spectrometry, the content of Cu was 36.2% by mass and the content of Zn was 36.2% by mass. 0.5 mass %.
• Example 2 Comparative Example 1
• the reaction was carried out in the same manner as in Example 1, except that the catalyst was changed as shown in Table 1.
• Table 1 shows the results.
• Example 3 to 5 Examination of molar ratio (first component/second component) Reaction was carried out in the same manner as in Example 1, except that the catalyst was changed as shown in Table 2. Table 2 shows the results.
• Example 9 Examination of raw material alcohol The reaction was carried out in the same manner as in Example 1, except that the catalyst, raw material alcohol, and reaction temperature were changed as shown in Table 4. Table 4 shows the results.
• Catalyst a1 used in Comparative Example 1 has almost the same content of the first component as catalysts A1 and A2 used in Examples 1 and 2, but the molar ratio (first component/second component) is within the limits of the present invention. out of range.
• Examples 1 and 2 using catalysts A1 and A2 have lower selectivity for by-produced hydrocarbon compounds than Comparative Example 1 using catalyst a1, and improve the yield of Guerbet alcohols produced. It was found to be excellent in the effect of making
• Example 6 using catalyst A6 does not have a carrier, but Example 6 using catalyst A6 has a lower selectivity for by-produced hydrocarbon compounds than Comparative Example 1 using catalyst a1. Moreover, it turned out that it is excellent in the effect of improving the yield of Guerbet alcohols to generate
• Example 7 using catalyst A7 using hydrotalcite (HT) as a carrier and Example 8 using catalyst A8 using aluminum oxide (Al 2 O 3 ) as a carrier are comparative examples 1 using catalyst a1. It was found that the selectivity of hydrocarbon compounds produced as a by-product is low and the effect of improving the yield of Guerbet alcohols produced is excellent, as compared with .
• Example 9 using 1-dodecanol (C12) as the raw material alcohol is superior to Example 10 using 1-hexadecanol (C16) as the raw material alcohol in improving the yield of Guerbet alcohols produced. I found out.

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