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WO2024190649A1 - Catalyseur pour la production d'éther cyclique insaturé contenant un groupe alkyle, procédé pour la production d'éther cyclique insaturé contenant un groupe alkyle, et procédé pour la production d'éther cyclique saturé contenant un groupe alkyle - Google Patents

Catalyseur pour la production d'éther cyclique insaturé contenant un groupe alkyle, procédé pour la production d'éther cyclique insaturé contenant un groupe alkyle, et procédé pour la production d'éther cyclique saturé contenant un groupe alkyle Download PDF

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Publication number
WO2024190649A1
WO2024190649A1 PCT/JP2024/009000 JP2024009000W WO2024190649A1 WO 2024190649 A1 WO2024190649 A1 WO 2024190649A1 JP 2024009000 W JP2024009000 W JP 2024009000W WO 2024190649 A1 WO2024190649 A1 WO 2024190649A1
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Prior art keywords
cyclic ether
unsaturated cyclic
alkyl group
catalyst
group
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English (en)
Japanese (ja)
Inventor
裕子 高橋
郁也 飛田
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Mitsubishi Chemical Corp
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Mitsubishi Chemical Corp
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Priority to CN202480015542.8A priority Critical patent/CN120916840A/zh
Priority to JP2024518688A priority patent/JP7786568B2/ja
Priority to KR1020257033495A priority patent/KR20250160490A/ko
Publication of WO2024190649A1 publication Critical patent/WO2024190649A1/fr
Anticipated expiration legal-status Critical
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    • 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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B61/00—Other general methods
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/36—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms

Definitions

  • the present invention relates to a catalyst for producing alkyl group-containing cyclic ethers, a method for producing alkyl group-containing cyclic ethers, and a method for producing alkyl group-containing saturated cyclic ethers.
  • alkyl group-containing saturated cyclic ethers Saturated cyclic ethers containing alkyl groups
  • 2MeTHF 2-methyltetrahydrofuran
  • alkyl group-containing saturated cyclic ethers Saturated cyclic ethers containing alkyl groups
  • 2MeTHF 2-methyltetrahydrofuran
  • alkyl group-containing saturated cyclic ethers Saturated cyclic containing saturated cyclic ethers containing alkyl groups
  • 2MeTHF 2-methyltetrahydrofuran
  • alkyl group-containing saturated cyclic ethers especially 2-methyltetrahydrofuran, have excellent compatibility with hydrocarbon compositions such as gasoline.
  • Alkyl group-containing saturated cyclic ethers have excellent oxidation and vapor pressure properties. For this reason, they are used as additives to mobile fuels such as gasoline.
  • alkyl group-containing saturated cyclic ethers such as 2-MeTHF
  • unsaturated cyclic ethers having a formyl group or a hydroxymethyl group, such as furfural, which correspond to the cyclic ether in question (hereinafter referred to as "formyl group- or hydroxymethyl group-containing unsaturated cyclic ethers"), are used as starting materials.
  • Patent Document 1 discloses a technology in which furfural is hydrogenated in a continuous gas-phase reaction in the presence of a copper catalyst to produce 2-methylfuran (2MeF), an unsaturated cyclic ether containing an alkyl group (hereinafter referred to as "alkyl-containing unsaturated cyclic ether").
  • 2MeF 2-methylfuran
  • alkyl-containing unsaturated cyclic ether an unsaturated cyclic ether containing an alkyl group
  • Patent Document 2 discloses a technology for producing 2-MeTHF by hydrogenating furfural through a continuous gas-phase reaction in the presence of a Pd/C catalyst.
  • An object of the present invention is to provide a catalyst for producing an alkyl group-containing unsaturated cyclic ether, which can carry out a reaction in a liquid phase when producing an alkyl group-containing unsaturated cyclic ether, such as 2-methylfuran, using a formyl group- or hydroxymethyl group-containing cyclic ether, such as furfural, as a starting material, and which can produce an alkyl group-containing unsaturated cyclic ether, such as 2-methylfuran, in high yield with fewer by-products, as compared with conventional techniques.
  • Another object of the present invention is to provide a method for producing an alkyl group-containing unsaturated cyclic ether, such as 2-methylfuran, from a formyl group- or hydroxymethyl group-containing unsaturated cyclic ether, such as furfural, by using the catalyst for producing an alkyl group-containing unsaturated cyclic ether.
  • an alkyl group-containing unsaturated cyclic ether such as 2-methylfuran
  • a further object of the present invention is to provide a method for producing an alkyl group-containing saturated cyclic ether, which uses an alkyl group-containing unsaturated cyclic ether such as 2-methylfuran obtained by the method for producing an alkyl group-containing unsaturated cyclic ether corresponding to the alkyl group-containing unsaturated cyclic ether, such as 2-methyltetrahydrofuran.
  • the present inventors have found that the above-mentioned problems can be solved by using a catalyst containing ruthenium and at least either tin or platinum as a catalyst for producing an alkyl group-containing unsaturated cyclic ether, such as 2-methylfuran, from a formyl group- or hydroxymethyl group-containing unsaturated cyclic ether, such as furfural.
  • a catalyst containing ruthenium and at least either tin or platinum as a catalyst for producing an alkyl group-containing unsaturated cyclic ether, such as 2-methylfuran, from a formyl group- or hydroxymethyl group-containing unsaturated cyclic ether, such as furfural.
  • a catalyst for producing an alkyl group-containing unsaturated cyclic ether (2) from an unsaturated cyclic ether (1) having a formyl group or a hydroxymethyl group comprising: A catalyst for producing an alkyl group-containing unsaturated cyclic ether, which contains ruthenium and at least one of tin and platinum.
  • a method for producing an alkyl group-containing unsaturated cyclic ether comprising a reaction step of subjecting an unsaturated cyclic ether (1) having a formyl group or a hydroxymethyl group to a hydrodeoxygenation reaction in the presence of a catalyst according to any one of [1] to [5] to obtain an alkyl group-containing unsaturated cyclic ether (2).
  • a method for producing an alkyl group-containing saturated cyclic ether comprising: a hydrodeoxygenation step of obtaining an alkyl group-containing unsaturated cyclic ether by the method for producing an alkyl group-containing unsaturated cyclic ether according to any one of [6] to [9]; and a hydrogenation step of hydrogenating the obtained alkyl group-containing unsaturated cyclic ether in the presence of a precious metal catalyst containing at least one selected from Group 8 precious metals and Group 10 precious metals of the long periodic table of the elements, to obtain an alkyl group-containing saturated cyclic ether.
  • a method for producing an alkyl group-containing saturated cyclic ether comprising obtaining an alkyl group-containing unsaturated cyclic ether by the method for producing an alkyl group-containing unsaturated cyclic ether according to any one of [6] to [9], and adding a precious metal catalyst containing at least one selected from the group 8 precious metals and group 10 precious metals of the long periodic table of the elements to the obtained alkyl group-containing unsaturated cyclic ether to effect a hydrogenation reaction to obtain an alkyl group-containing saturated cyclic ether.
  • the present invention provides a catalyst for producing alkyl group-containing unsaturated cyclic ethers that can carry out a reaction in the liquid phase, produce fewer by-products, and produce alkyl group-containing unsaturated cyclic ethers such as 2-methylfuran from formyl group- or hydroxymethyl group-containing unsaturated cyclic ethers such as furfural in high yields, compared to conventional techniques.
  • the catalyst for producing alkyl group-containing unsaturated cyclic ethers of the present invention can carry out a reaction in the liquid phase, and therefore does not require the above-mentioned excessively large high-pressure gas equipment, and production costs can be reduced, compared to the conventional methods using gaseous raw materials.
  • the catalyst for producing alkyl group-containing unsaturated cyclic ethers of the present invention can suppress the by-production of 1-pentanol or 1,2-pentanediol due to the ring-opening reaction of the furan ring, compared to the copper-based catalysts of the conventional technology, and can produce alkyl group-containing unsaturated cyclic ethers such as 2-methylfuran in higher yields.
  • alkyl group-containing saturated cyclic ethers such as 2-methyltetrahydrofuran
  • alkyl group-containing unsaturated cyclic ethers such as 2-methylfuran produced by the method for producing alkyl group-containing unsaturated cyclic ethers of the present invention using the catalyst for producing alkyl group-containing unsaturated cyclic ethers.
  • a numerical range expressed using “ ⁇ ” means a range that includes the numerical values written before and after “ ⁇ ” as the lower and upper limits, and "A ⁇ B" means greater than or equal to A and less than or equal to B.
  • a or B means “A”, “B”, and “A and B”, unless otherwise specified.
  • including A or B means “including A”, “including B”, and “including A and B”, unless otherwise specified.
  • mass % indicates the content ratio of a given component contained in a total amount of 100 mass %.
  • mass% and weight% are synonymous. When simply written as “ppm”, it means “ppm by mass”.
  • the term "about” means 20% above or below the stated value.
  • about 75°C includes the range of 60°C to 90°C.
  • the catalyst for producing an alkyl group-containing unsaturated cyclic ether of the present invention (hereinafter sometimes referred to as "the catalyst") is a catalyst used for producing an alkyl group-containing unsaturated cyclic ether (2).
  • the catalyst is a catalyst used in a process for producing an alkyl group-containing, particularly a methyl group-containing unsaturated cyclic ether (2) corresponding to the unsaturated cyclic ether (1) from a formyl group- or hydroxymethyl group-containing unsaturated cyclic ether (1), and contains ruthenium and at least either tin or platinum (hereinafter sometimes abbreviated as "Ru/Sn.Pt").
  • tin and platinum when the phrase "at least one of tin and platinum" is used, either tin or platinum may be used, or both tin and platinum may be used. Among these, the use of both tin and platinum in combination with ruthenium is preferred from the viewpoint of the yield of the target product.
  • this catalyst contains Ru/Sn.Pt, it is suitable as a catalyst for use in the production of alkyl group-containing unsaturated cyclic ether (2). Specifically, by using this catalyst as a catalyst for producing alkyl group-containing unsaturated cyclic ether (2) corresponding to unsaturated cyclic ether (1) from formyl group- or hydroxymethyl group-containing unsaturated cyclic ether (1), the unsaturated cyclic ether (2) can be produced with few by-products and in high yield.
  • This catalyst is usually used as a metal-supported catalyst in which the Ru/Sn.Pt is supported on a carrier.
  • This catalyst is usually produced by subjecting a metal-supported material in which Ru/Sn.Pt is supported on a carrier to a reduction treatment using a reducing gas, followed by an oxidation stabilization treatment.
  • the catalytically active components in the present catalyst include ruthenium and at least either tin or platinum (Ru/Sn.Pt).
  • the mass ratio of tin and platinum to ruthenium in the present catalyst is not particularly limited. From the viewpoint of producing the unsaturated cyclic ether (2) with a small amount of by-products and in a high yield, this mass ratio is preferably 0.4 to 1.8, more preferably 0.45 to 1.5, and even more preferably 0.5 to 1.2. If this mass ratio is within the above range, the effects of the present invention achieved by using ruthenium in combination with at least one of tin and platinum can be effectively obtained.
  • the catalyst of the present invention may contain Ru/Sn.Pt as an essential component, and may further contain other metals as necessary, in addition to Ru/Sn.Pt, as long as the effect of the present invention is not impaired.
  • the other metals are not particularly limited.
  • the other metals are preferably at least one selected from metal species such as rhodium, gold, molybdenum, tungsten, rhenium, barium, and boron, and more preferably at least one selected from rhenium and gold.
  • the present catalyst can obtain sufficiently high catalytic activity by using Ru/Sn.Pt.
  • the lower limit of the content of the other metal components relative to the total mass of Ru/Sn.Pt and the other metal components (100%) is not particularly limited, but from the viewpoint of producing the unsaturated cyclic ether (2) with a small amount of by-products and in a high yield, it is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and preferably 1.0% by mass or more.
  • the upper limit of the content of the other metal components is not particularly limited, but is preferably 10% by mass or less, more preferably 5% by mass or less, and preferably 3% by mass or less. The above upper and lower limits can be combined in any manner.
  • the present catalyst can be used as a Ru/Sn.Pt supported catalyst in which Ru/Sn.Pt is supported on a support.
  • the Ru/Sn.Pt supported catalyst is easy to handle, and can exert catalytic function not only on the surface of the Ru/Sn.Pt supported catalyst, but also in the pores in which Ru/Sn.Pt is supported. For this reason, it is preferable from the viewpoint of improving the conversion rate of the raw material unsaturated cyclic ether (1) and the selectivity of the target product unsaturated cyclic ether (2).
  • the type of carrier used in the present catalyst is not particularly limited.
  • carriers that can be used include carbonaceous carriers such as activated carbon and carbon black; silica, diatomaceous earth; inorganic porous carriers of oxide-based ceramics such as silicon oxide, alumina, zirconia, titania, and hafnia; silicon carbide; and gallium nitride. Of these, carbonaceous carriers are preferred, and activated carbon is more preferred.
  • the support may be used as is, or may be pretreated to a form suitable for support.
  • the carbonaceous support may be heat-treated with nitric acid before use, as described in JP-A-10-71332. This method is preferable because it improves the dispersibility of the metal components on the support and improves the activity of the resulting catalyst.
  • the shape of the carrier used in the present catalyst is not particularly limited, and examples thereof include powder, granules, pellets, etc. Among these, granules and pellets are preferred from the viewpoint of improving operability.
  • the size of the carrier used in the present catalyst is not particularly limited, but when converted into a spherical shape, the average particle size is usually 50 ⁇ m or more and 5 mm or less, and preferably 4 mm or less.
  • the particle size of the carrier is measured by the sieve analysis test method described in JIS standard JIS Z8815 (1994). By setting the average particle size within the above range, the catalyst has high activity per unit weight and is easy to handle.
  • the particle diameter of the carrier is usually 50 ⁇ m or more, preferably 100 ⁇ m or more, and usually 3 mm or less, preferably 2 mm or less.
  • the smaller the particle diameter of the carrier the higher the activity per unit mass of the resulting catalyst is, which is preferable. If the particle diameter of the carrier is too small below the lower limit, it may be difficult to separate the reaction liquid from the catalyst. If the shape of the carrier is not spherical, the particle diameter of the carrier is calculated by calculating the volume of the carrier and converting it into the diameter of a spherical particle of the same volume.
  • the particle size of the carrier is usually 0.5 mm or more and 5 mm or less, preferably 4 mm or less, and more preferably 3 mm or less. If the particle size is smaller than the lower limit, operation may become difficult due to the pressure difference. If the particle size is larger than the upper limit, the reaction activity may decrease.
  • the amount of Ru/Sn.Pt supported on the carrier in the present catalyst is not particularly limited.
  • the lower limit of the amount of ruthenium supported is usually 1 part by mass or more, preferably 3 parts by mass or more, based on the total mass of 100 parts by mass of the present catalyst.
  • the upper limit of the amount of Ru/Sn.Pt supported is usually 10 parts by mass or less, preferably 8 parts by mass or less, based on the total mass of 100 parts by mass of the present catalyst.
  • the above upper and lower limits can be combined in any combination.
  • the amount of Ru/Sn.Pt supported on the carrier in the present catalyst is usually 1 part by mass or more and 10 parts by mass or less, preferably 3 parts by mass or more and 8 parts by mass or less, relative to 100 parts by mass of the total mass of the present catalyst.
  • the lower limit of the amount of either or both of tin and platinum supported on the carrier in the present catalyst is usually 1 part by mass or more, preferably 2 parts by mass or more, per 100 parts by mass of the total mass of the present catalyst, while the upper limit of the amount of either or both of tin and platinum supported is usually 15 parts by mass or less, preferably 10 parts by mass or less, per 100 parts by mass of the total mass of the present catalyst.
  • the above upper and lower limits can be combined in any combination.
  • the amount of tin and/or platinum supported on the carrier in the present catalyst is usually 1 part by mass or more and 15 parts by mass or less, preferably 2 parts by mass or more and 10 parts by mass or less, per 100 parts by mass of the total mass of the present catalyst.
  • the amount of other metals supported is not particularly limited. As long as the effect of the present invention is not impaired, the amount of other metals supported can usually be 7 parts by mass or less, and preferably 5 parts by mass or less, per 100 parts by mass of the total mass of the catalyst.
  • the lower limit of the total amount of Ru/Sn.Pt and other metals supported is not particularly limited, but is usually 5 parts by mass or more, preferably 8 parts by mass or more, and more preferably 10 parts by mass or more, relative to 100 parts by mass of the total mass of the present catalyst.
  • the upper limit of the total amount of Ru/Sn.Pt and other metals supported is not particularly limited, but is usually 40 parts by mass or less, preferably 30 parts by mass or less, and more preferably 20 parts by mass or less, relative to 100 parts by mass of the total mass of the present catalyst.
  • the upper and lower limits can be combined in any combination.
  • the total amount of Ru/Sn.Pt and other metals supported is usually 5 parts by mass or more and 40 parts by mass or less, preferably 8 parts by mass or more and 30 parts by mass or less, and more preferably 10 parts by mass or more and 20 parts by mass or less, relative to 100 parts by mass of the total mass of the present catalyst.
  • the amount of supported metal is a value calculated assuming that all the supported metal is metal atoms.
  • the amount of supported metal can be measured, for example, by dissolving the metal components from the metal-supported catalyst using an acid and analyzing the concentration in the solution using atomic absorption spectrometry or inductively coupled plasma (ICP) optical emission spectrometry, or by crushing the metal-supported catalyst to 50 ⁇ m or less and then using X-ray fluorescence (XRF) analysis in the solid state.
  • ICP inductively coupled plasma
  • the present catalyst can be produced by optimizing, for example, the method for producing the catalyst described in paragraphs 0033 to 0079 of JP-A-2020-168628 by a person skilled in the art according to well-known techniques.
  • the formyl- or hydroxymethyl-containing unsaturated cyclic ether (1) to which the present catalyst is applied is not particularly limited, and examples thereof include 5- or 6-membered unsaturated cyclic ethers having a formyl or hydroxymethyl group, such as furan, pyran, dihydropyran, etc.
  • furfural, dihydropyran, etc. are preferred, and furfural is most preferred.
  • alkyl group-containing unsaturated cyclic ether (2) The alkyl group-containing unsaturated cyclic ether (2) produced from the formyl group- or hydroxymethyl group-containing unsaturated cyclic ether (1) by the present catalyst is a product in which the formyl group or hydroxymethyl group is converted to a methyl group by hydrodeoxygenation of the formyl group- or hydroxymethyl group-containing unsaturated cyclic ether (1).
  • Specific examples include 2-methylfuran and 2-methyl-2,3-dihydro-4H-pyran. For the same reasons as above, 2-methylfuran is most preferred.
  • This catalyst is suitable as a catalyst for producing 2-methylfuran as an alkyl group-containing unsaturated cyclic ether (2) from furfural as a formyl group- or hydroxymethyl group-containing unsaturated cyclic ether (1).
  • the method for producing an alkyl group-containing unsaturated cyclic ether of the present invention is a method for producing an alkyl group-containing unsaturated cyclic ether (2), comprising a reaction step of subjecting a formyl group- or hydroxymethyl group-containing unsaturated cyclic ether (1) to a hydrodeoxygenation reaction in the presence of the present catalyst to obtain an alkyl group-containing unsaturated cyclic ether (2) corresponding to the formyl group- or hydroxymethyl group-containing unsaturated cyclic ether (1).
  • the method for producing an alkyl group-containing unsaturated cyclic ether (2) using the present catalyst is not particularly limited as long as it proceeds in the presence of the present catalyst.
  • the method for producing an alkyl group-containing unsaturated cyclic ether (2) using the present catalyst is preferably a heterogeneous reaction in which a formyl group- or hydroxymethyl group-containing unsaturated cyclic ether (1), the present catalyst, and hydrogen are contacted in a continuous or batchwise manner to carry out a hydrodeoxygenation reaction.
  • the hydrodeoxygenation reaction may be a gas-liquid-solid three-phase reaction carried out by contacting liquid formyl- or hydroxymethyl-group-containing unsaturated cyclic ether (1) or a solution containing formyl- or hydroxymethyl-group-containing unsaturated cyclic ether (1) with hydrogen (hydrogen gas), or may be a gas-solid two-phase reaction in which gaseous (vaporized) formyl- or hydroxymethyl-group-containing unsaturated cyclic ether (1) is reacted with hydrogen.
  • the solvent used in the liquid phase reaction can be appropriately selected depending on the type of formyl group- or hydroxymethyl group-containing unsaturated cyclic ether (1) and is not particularly limited. If water is used as the solvent, polymerization and rearrangement reactions tend to proceed, but the hydrodeoxygenation reaction does not proceed. For this reason, it is preferable to use an organic solvent.
  • the organic solvent used in the hydrodeoxygenation reaction in the present invention is not particularly limited, but examples thereof include the following: Ether compounds such as dioxane and 2-methyltetrahydrofuran; ester compounds such as ethyl acetate and butyl acetate; Alcohol compounds such as methanol, ethanol, isopropanol, n-butanol, and 2-butanol; Aliphatic hydrocarbon compounds such as hexane, heptane, and octane; Alicyclic hydrocarbon compounds such as cyclohexane; Aromatic hydrocarbon compounds such as benzene, toluene, xylene, and ethylbenzene; Halogenated hydrocarbon compounds such as chloroform, methylene chloride, and 1,2-dichloroethane; Nitrile compounds such as acetonitrile, propionitrile, and benzonitrile. These organic solvents may be used alone or in combination of two or more.
  • ether compounds, alcohol compounds, and ester compounds are preferred from the standpoint of ease of separation from the product, economy, and toxicity, with ether compounds and alcohol compounds being particularly preferred.
  • the amount of the organic solvent used is not particularly limited.
  • the amount of the organic solvent used can be appropriately selected from a range such that the concentration of the formyl group- or hydroxymethyl group-containing unsaturated cyclic ether (1) when the formyl group- or hydroxymethyl group-containing unsaturated cyclic ether (1) is dissolved before the hydrodeoxygenation reaction is 5 to 80% by mass, particularly 20 to 60% by mass.
  • the lower limit of the amount of the catalyst used in the hydrodeoxygenation reaction is not particularly limited, but from the viewpoint of reaction rate, it is preferably 2% by mass or more, more preferably 5% by mass or more, and even more preferably 8% by mass or more, calculated as Ru/Sn.Pt metals relative to the formyl group- or hydroxymethyl group-containing unsaturated cyclic ether (1).
  • the upper limit of the amount of the catalyst used is not particularly limited, but from the viewpoint of economy, it is preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 18% by mass or less, calculated as Ru/Sn.Pt metals relative to the formyl group- or hydroxymethyl group-containing unsaturated cyclic ether (1).
  • the above upper and lower limits can be combined in any combination.
  • the amount of the catalyst used in the hydrodeoxygenation reaction is preferably 2 to 25 mass %, more preferably 5 to 20 mass %, and even more preferably 8 to 18 mass %, calculated as the metal amount of Ru/Sn.Pt, relative to the amount of the formyl group- or hydroxymethyl group-containing unsaturated cyclic ether (1).
  • the ratio of hydrogen to the formyl- or hydroxymethyl-containing unsaturated cyclic ether (1) used in the hydrodeoxygenation reaction is not particularly limited and can be set appropriately depending on the reaction format employed, etc.
  • components other than the formyl group- or hydroxymethyl group-containing unsaturated cyclic ether (1), the catalyst, and hydrogen can also be present within a range that does not impair the effects of the present invention.
  • the lower limit of the reaction temperature in the hydrodeoxygenation reaction is not particularly limited, but if the reaction temperature is too low, the hydrodeoxygenation reaction cannot proceed smoothly. Therefore, the reaction temperature is preferably 185°C or higher, more preferably 190°C or higher, and even more preferably 200°C or higher.
  • the upper limit of the reaction temperature is not particularly limited, but if the reaction temperature is too high, side reactions tend to proceed. Therefore, the reaction temperature is preferably 240°C or lower, more preferably 230°C or lower, and even more preferably 220°C or lower.
  • the above upper and lower limits can be combined in any combination.
  • the reaction temperature in the hydrodeoxygenation reaction is not particularly limited, but is preferably 185° C.
  • reaction temperature may be controlled so as to always be constant (substantially constant) during the hydrodeoxygenation reaction, or may be controlled so as to change stepwise or continuously.
  • the reaction time for the hydrodeoxygenation reaction is not particularly limited and can be set appropriately depending on the reaction type employed, etc.
  • the lower limit of the reaction pressure in the hydrodeoxygenation reaction is not particularly limited, but is usually 0.1 MPa or more, more preferably 1.0 MPa or more, while the upper limit of the reaction pressure is not particularly limited, but is usually 20 MPa or less, more preferably 10 MPa or less.
  • the above upper and lower limits can be combined in any combination.
  • the reaction pressure in the hydrodeoxygenation reaction is not particularly limited, but is usually 0.1 to 20 MPa, and more preferably 1 to 10 MPa.
  • the reaction pressure may be controlled so as to be always constant (substantially constant) during the hydrodeoxygenation reaction, or may be controlled so as to change stepwise or continuously.
  • the hydrodeoxygenation reaction can be carried out in any manner, such as batchwise, semi-batchwise, or continuous (continuous flow) manner.
  • alkyl group-containing unsaturated cyclic ether (2) obtained from a given amount of formyl group- or hydroxymethyl group-containing unsaturated cyclic ether (1)
  • a process may be employed in which the unreacted formyl group- or hydroxymethyl group-containing unsaturated cyclic ether (1) remaining after the reduction reaction is carried out is separated, recovered, and recycled.
  • a known or conventional reactor can be used as the reactor.
  • a batch reactor, a fluidized bed reactor, a fixed bed reactor, etc. can be used.
  • the method for producing an alkyl group-containing unsaturated cyclic ether of the present invention may include, in addition to the hydrodeoxygenation reaction, other steps as necessary.
  • other steps include a step of preparing and purifying a solution of the raw material formyl group- or hydroxymethyl group-containing unsaturated cyclic ether (1), a step of separating the reaction product discharged (flowing out) from the reactor (e.g., a mixture containing alkyl group-containing unsaturated cyclic ether (2), hydrogen, and formyl group- or hydroxymethyl group-containing unsaturated cyclic ether (1), by-products, etc.) to purify the target product, and a step of regenerating the catalyst.
  • These steps may be carried out in a separate line from the hydrodeoxygenation reaction, or may be carried out as a series of steps (in-line).
  • the alkyl group-containing unsaturated cyclic ether (2) obtained by the method for producing an alkyl group-containing unsaturated cyclic ether of the present invention can be purified by known or conventional methods (e.g., distillation, adsorption, ion exchange, crystallization, extraction, etc.).
  • the following methods can be used to recover the target item:
  • the reaction product obtained in the hydrodeoxygenation step is condensed by cooling in a known technique, preferably in a heat exchanger. Condensation causes phase separation.
  • the lower phase obtained by phase separation consists of more than 90% water.
  • the upper phase obtained by phase separation contains the desired alkyl group-containing unsaturated cyclic ether (2) and a small amount of by-products, which can be efficiently separated and removed by a subsequent distillation separation or the like.
  • the alkyl group-containing unsaturated cyclic ether (2) can be obtained in very good yield and purity by the method according to the present invention.
  • Phase separation can be carried out at room temperature (about 25°C), but since the alkyl group-containing unsaturated cyclic ether (2) has a lower solubility in water at lower temperatures, it is preferable to carry out phase separation at 20°C or lower, for example, at 5 to 15°C.
  • the upper phase containing the alkyl group-containing unsaturated cyclic ether (2) which is the target product obtained by phase separation, can be distilled, for example, using a packed column containing packing materials such as metal rings, to recover high-purity alkyl group-containing unsaturated cyclic ether (2).
  • this distillation step is not necessarily required.
  • the reaction product liquid obtained in the hydrodeoxygenation reaction may be directly supplied to the subsequent hydrogenation reaction step.
  • a first embodiment of the method for producing an alkyl group-containing saturated cyclic ether of the present invention includes a step of obtaining an alkyl group-containing unsaturated cyclic ether (2) by the method for producing an alkyl group-containing unsaturated cyclic ether of the present invention, and a hydrogenation step of hydrogenating the obtained alkyl group-containing unsaturated cyclic ether (2) in the presence of a precious metal catalyst containing at least one selected from the group consisting of Group 8 precious metals and Group 10 precious metals of the Periodic Table of the Elements to obtain an alkyl group-containing saturated cyclic ether corresponding to the alkyl group-containing unsaturated cyclic ether (2) (hereinafter sometimes referred to as "alkyl group-containing saturated cyclic ether (3)").
  • a second embodiment of the method for producing an alkyl group-containing saturated cyclic ether of the present invention includes obtaining an alkyl group-containing unsaturated cyclic ether by the method for producing an alkyl group-containing unsaturated cyclic ether of the present invention, and adding a catalyst containing at least one selected from the group 8 noble metals and group 10 noble metals of the long periodic table of the elements to the obtained alkyl group-containing unsaturated cyclic ether to carry out a hydrogenation reaction to obtain an alkyl group-containing saturated cyclic ether (3).
  • the precious metal of the precious metal catalyst containing at least one selected from the group 8 and group 10 precious metals of the long periodic table of the elements used in the hydrogenation reaction is preferably rhodium, ruthenium, platinum, palladium, iridium, osmium, etc.
  • ruthenium, rhodium, and palladium are particularly preferred from the viewpoints of reactivity and selectivity.
  • the noble metal catalyst include metal compounds such as zero-valent noble metals, or various inorganic compounds such as nitrates, sulfates, acetates, chlorides, bromides, oxides, and hydroxides of noble metals; carrier-supported catalysts in which noble metals are supported on a carrier; various organic compounds such as acetylacetonate compounds; and various complex compounds such as amine complexes, phosphine complexes, and carbonyl compounds. These may be used alone or in combination of two or more.
  • precious metal supported catalysts include Ru-carbon catalysts, Rh-carbon catalysts, Pd-carbon catalysts, Ru-alumina catalysts, Rh-alumina catalysts, and Pd-alumina catalysts. Among these, Pd-carbon catalysts and Pd-alumina catalysts are particularly preferred.
  • the water content of the precious metal-supported catalyst is not particularly limited, and both dry and wet products can be used.
  • the form of the noble metal catalyst in the present invention is not particularly limited, and may be appropriately selected from powder, molded catalyst, etc. depending on the reaction method to be selected. Powdered catalysts are typically used in batch or continuous liquid phase slurry bed hydrogenation reactions.
  • the molded catalyst is used in the hydrogenation reaction in a fixed bed flow system.
  • the molded catalyst is appropriately selected depending on the size of the reactor to be used.
  • the molded catalyst is preferably cylindrical, usually with a diameter of 2 to 6 mm and a height of 2 to 8 mm.
  • the above-mentioned supported catalysts can be prepared by conventional methods such as impregnation and coprecipitation. There are no particular limitations on the method of activating these supported catalysts, but they are usually activated by reduction before use.
  • the amount of the noble metal catalyst used in the hydrogenation reaction is preferably in the range of 0.0005 to 5 parts by mass, preferably 0.005 to 3 parts by mass, and more preferably 0.01 to 2 parts by mass, based on the metal content per 100 parts by mass of the total mass of the alkyl group-containing unsaturated cyclic ether (2), from the standpoint of reaction speed and economy.
  • the hydrogenation reaction according to the present invention can be carried out either without a solvent or in the presence of a solvent.
  • the solvent that can be used is not particularly limited as long as it does not adversely affect the hydrogenation reaction.
  • reaction solvent examples include water; Known alcohol solvents such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, hexanol, heptanol, octanol, propylene glycol, ethylene glycol, diethylene glycol, tetraethylene glycol, glycerin, 1,3-propanediol, and cyclohexanol; Known ether solvents such as diethyl ether, diisopropyl ether, dibutyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane, 1,3-dioxane, and 1,4-dioxane; Known aliphatic hydrocarbon solvents such as n-pentane
  • the hydrogen partial pressure in the hydrogenation reaction according to the present invention is not particularly limited as long as the hydrogenation reaction can be completed. Under conditions that allow a practical reaction rate, the hydrogen partial pressure in the reaction system is usually in the range of 0.1 to 30 MPa, preferably 0.1 to 10 MPa. If the hydrogen partial pressure is lower than 0.1 MPa, the reaction takes longer than necessary. If the hydrogen partial pressure exceeds 30 MPa, the reaction rate increases, but if the pressure is too high, no significant advantage is observed and it may be economically disadvantageous.
  • the reaction temperature is not particularly limited as long as the hydrogenation reaction can be completed. In order to obtain a practical reaction rate, the reaction temperature is usually 20 to 200°C, and preferably 40 to 180°C. If the temperature is lower than this range, a sufficient reaction rate cannot be obtained. If the temperature is higher than this range, side reactions and decomposition reactions occur, which tends to reduce the yield.
  • the reaction time varies depending on the amount of catalyst and other conditions.
  • the reaction time is usually about 0.5 to 50 hours, and from an industrial standpoint, it is preferable to select conditions so that the reaction time is 1 to 20 hours.
  • the reaction method of the hydrogenation reaction according to the present invention is not particularly limited.
  • the reaction method may be a liquid-phase suspension bed method in which a precious metal catalyst is dispersed in a reaction liquid, or a fixed-bed flow method in which a precious metal catalyst is fixed in a reactor and the reaction liquid is allowed to act on the catalyst.
  • the catalyst can be removed using a conventional method such as filtration or centrifugation to obtain the alkyl group-containing saturated cyclic ether (3).
  • the alkyl group-containing saturated cyclic ether (3) can be purified by distillation or the like to obtain a highly pure alkyl group-containing saturated cyclic ether (3).
  • the reaction product liquid containing the alkyl group-containing saturated cyclic ether (3) obtained in the hydrogenation reaction according to the present invention can be subjected to phase separation and distillation in the same manner as in the reaction product liquid containing the alkyl group-containing unsaturated cyclic ether (2) described above, to recover the desired alkyl group-containing saturated cyclic ether (3).
  • the alkyl group-containing saturated cyclic ether (3) produced by the method for producing an alkyl group-containing saturated cyclic ether of the present invention is a saturated cyclic ether produced by adding a hydrogen atom to the double bond of the unsaturated cyclic ether of the alkyl group-containing unsaturated cyclic ether (2) produced by the method for producing an alkyl group-containing unsaturated cyclic ether of the present invention.
  • the alkyl group-containing saturated cyclic ether (3) produced is preferably 2-methyltetrahydrofuran.
  • the method for producing alkyl group-containing saturated cyclic ethers of the present invention is extremely useful industrially as a method for producing 2-methylfuran by a hydrodeoxygenation reaction using furfural as a starting material and the catalyst, and then producing 2-methyltetrahydrofuran by a hydrogenation reaction of 2-methylfuran.
  • evaluation method In the following, the evaluation methods for each physical property value are as follows.
  • the reaction liquids obtained in the examples and comparative examples were analyzed for composition using a gas chromatograph (GC) under the following measurement conditions to determine the raw material furfural (FA), the target products 2-methylfuran (2MeF) and 2-methyltetrahydrofuran (2MeTHF), the by-products 1-pentanol (1POL), furfuryl alcohol (FOL), 2-methylhydroxytetrahydrofuran (THFOL), 1,2-pentanediol (12PDOL), 1,4-pentanediol (14PDOL), and other impurities.
  • the other impurities include decomposition or alteration products of FA, and polymerized products of FOL.
  • GC measurement conditions GC device: GC-2014 (device name, manufactured by Shimadzu Corporation) Detector: Flame ionization detector (FID) Carrier gas: Helium (flow rate 1 ml/min) Column: Capillary column DB-1 (Agilent Technologies, size: length 60 m x inner diameter 0.25 mm, film thickness 0.25 ⁇ m) Column temperature: 50°C (holding time 5 minutes) ⁇ heating at 5°C/min ⁇ 150°C (no holding time) ⁇ heating at 15°C/min ⁇ 300°C (no holding time) Inlet temperature: 250°C Detector temperature: 300°C Sample volume: 1 ⁇ L (split ratio: 1/20) Quantitative method: Internal standard method using diglyme as the internal standard substance
  • Catalyst A was produced using a 1 mm cylindrical activated carbon carrier (product name: Norit R1 EXTRA, manufactured by NORIT Co., Ltd.) according to the method described in Example 4 of JP-A No. 2001-9277.
  • aqueous solution of metal chlorides containing ruthenium chloride hydrate, chloroplatinic acid (IV) hexahydrate, and tin (II) chloride dihydrate Using an aqueous solution of metal chlorides containing ruthenium chloride hydrate, chloroplatinic acid (IV) hexahydrate, and tin (II) chloride dihydrate, the ruthenium, platinum, and tin in the metal chlorides were supported on the activated carbon to prepare a metal-supported material (hereinafter referred to as "metal-supported material 1").
  • the amount of the aqueous metal chloride solution used for impregnating the activated carbon was set to be the same as the pore volume of the activated carbon.
  • the treated metal-supported material 1 (about 2 g) was dried at 150° C. for 2 hours under an argon flow (5 L/h), and then reduced at 500° C. for 2 hours under a hydrogen flow (5 L/h). Thereafter, the metal oxide was oxidized and stabilized under a nitrogen flow (2 L/h) with an oxygen concentration of 5.0% to obtain a metal oxide, which was used as catalyst A.
  • the amount of each metal element was set so that when the entire amount was supported, hydrogen reduced, and oxidized and stabilized, the total mass of the carbonaceous support was 100 parts by mass, and the amount of Ru was 5.5 parts by mass, Pt was 2.4 parts by mass, and Sn was 6.4 parts by mass (the mass ratio of tin and platinum to ruthenium was 1.6).
  • a metal oxide was prepared as catalyst C in the same manner as in Reference Example 1, except that silica gel (product name: CARiACT Q-15, manufactured by Fuji Silysia Chemical Ltd.) was used as a carrier and the treatment with ammonium bicarbonate was not carried out.
  • the amounts of the metal elements were such that, when the entire amounts were supported, reduced with hydrogen, and stabilized by oxidation, the amounts of Ru were 5.5 parts by mass, Pt was 2.4 parts by mass, and Sn was 6.4 parts by mass (the weight ratio of tin and platinum to ruthenium was 1.6) relative to 100 parts by mass of the total mass of the silica gel carrier.
  • the amounts of the metal elements were such that, when the entire amounts were supported, reduced with hydrogen, and oxidized and stabilized, the amounts of Ru were 5.5 parts by mass, Pt was 2.4 parts by mass, and Sn was 6.4 parts by mass (the mass ratio of tin and platinum to ruthenium was 1.6) relative to 100 parts by mass of the total mass of the alumina support.
  • Example 1 Production of 2MeF
  • a 70 mL spinner-stirred autoclave AC
  • 1.00 g of FA, 4.00 g of dioxane as a solvent, and 0.6 g of catalyst A were charged.
  • the operation of replacing the inside of the AC with nitrogen gas pressure 1 MPa
  • the operation of replacing the inside of the AC with hydrogen gas pressure 3 MPa
  • the temperature in the AC was raised to 200°C, and then the hydrogen deoxygenation reaction of FA was carried out for 2 hours.
  • the temperature in the AC was cooled to room temperature (25°C), and the inside of the AC was replaced with nitrogen. While the inside of the AC was replaced with nitrogen, the reaction liquid was extracted from the bottom of the AC.
  • the obtained reaction liquid was analyzed by gas chromatography, and it was confirmed that 2MeF was produced.
  • the analysis results are shown in Table 1.
  • Example 2 and Comparative Examples 1 to 6 Types of Catalysts] 2MeF was produced in the same manner as in Example 1, except that the type of catalyst and the reaction temperature were changed as shown in Table 1. The analytical results are shown in Table 1.
  • the support was not a carbonaceous support but silica, so the yield of 2MeF was low. The production of alcohols as by-products was small, and the yield of FOL, which was an intermediate, was high.
  • the support was alumina (Al 2 O 3 ) instead of a carbonaceous support, and therefore the yield of 2MeF was low. This is presumably because alumina has acid sites, which led to side reactions such as polymerization of the raw materials and intermediates.
  • Examples 3 to 5 and Comparative Example 9 Types of Solvents] 2MeF was produced in the same manner as in Example 1, except that the solvent in Example 1 was changed to one shown in Table 3. The analytical results are shown in Table 3. Table 3 also shows the results of Example 1.
  • Example 6 to 7 and Comparative Example 10 Reaction temperature
  • 2MeF was produced in the same manner as in Example 1, except that the reaction temperature in Example 1 was changed as shown in Table 4.
  • the analytical results are shown in Table 4.
  • Table 4 also shows the results of Example 1.
  • Example 9 Preparation of 2MeTHF
  • 0.1 g of 5% Pd carbon catalyst was added to the reaction solution in the AC.
  • the operation of replacing the inside of the AC with nitrogen gas pressure 1 MPa
  • the operation of replacing the inside of the AC with hydrogen gas pressure 3 MPa
  • the temperature in the AC was raised to 180°C, and then the hydrogenation reaction of 2MeF in the reaction solution was carried out for 2 hours.
  • the temperature in the AC was cooled to room temperature (25°C), and the inside of the AC was replaced with nitrogen. While the inside of the AC was replaced with nitrogen, the reaction solution was extracted from the bottom of the AC.
  • the obtained reaction solution was analyzed by gas chromatography, and it was confirmed that 2MeTHF was produced.
  • the yield of 2MeTHF was 81.3%.

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Abstract

L'invention concerne un catalyseur pour la production d'un éther cyclique insaturé contenant un groupe alkyle, le catalyseur étant utilisé pour la production d'un éther cyclique insaturé contenant un groupe alkyle (2) à partir d'un éther cyclique insaturé (1) qui possède un groupe formyle ou un groupe hydroxyméthyle, et le catalyseur contenant du ruthénium et au moins un élément parmi soit l'étain soit le platine. L'invention concerne également un procédé pour la production d'un éther cyclique insaturé contenant un groupe alkyle, le procédé comprenant une étape de réaction pour mettre en œuvre une réaction d'hydrogénation et de désoxygénation, en présence du catalyseur susmentionné, sur un éther cyclique insaturé (1) qui possède un groupe formyle ou un groupe hydroxyméthyle afin d'obtenir un éther cyclique insaturé contenant un groupe alkyle (2).
PCT/JP2024/009000 2023-03-10 2024-03-08 Catalyseur pour la production d'éther cyclique insaturé contenant un groupe alkyle, procédé pour la production d'éther cyclique insaturé contenant un groupe alkyle, et procédé pour la production d'éther cyclique saturé contenant un groupe alkyle Pending WO2024190649A1 (fr)

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CN202480015542.8A CN120916840A (zh) 2023-03-10 2024-03-08 含烷基的不饱和环状醚制造用催化剂、含烷基的不饱和环状醚的制造方法以及含烷基的饱和环状醚的制造方法
JP2024518688A JP7786568B2 (ja) 2023-03-10 2024-03-08 アルキル基含有不飽和環状エーテル製造用触媒、アルキル基含有不飽和環状エーテルの製造方法、及びアルキル基含有飽和環状エーテルの製造方法
KR1020257033495A KR20250160490A (ko) 2023-03-10 2024-03-08 알킬기 함유 불포화 환상 에테르 제조용 촉매, 알킬기 함유 불포화 환상 에테르의 제조 방법, 및 알킬기 함유 포화 환상 에테르의 제조 방법

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