WO2019240009A1 - Procédé de production de 1,3-butylène glycol - Google Patents

Procédé de production de 1,3-butylène glycol Download PDF

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Publication number
WO2019240009A1
WO2019240009A1 PCT/JP2019/022563 JP2019022563W WO2019240009A1 WO 2019240009 A1 WO2019240009 A1 WO 2019240009A1 JP 2019022563 W JP2019022563 W JP 2019022563W WO 2019240009 A1 WO2019240009 A1 WO 2019240009A1
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Prior art keywords
butylene glycol
reaction
butanone
hydroxy
producing
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PCT/JP2019/022563
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English (en)
Japanese (ja)
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耕平 立花
大島　俊二
太一 島田
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Jnc株式会社
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Priority to JP2020525503A priority Critical patent/JPWO2019240009A1/ja
Publication of WO2019240009A1 publication Critical patent/WO2019240009A1/fr

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    • 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
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/143—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
    • C07C29/145—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones with hydrogen or hydrogen-containing gases
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/18—Polyhydroxylic acyclic alcohols
    • C07C31/20—Dihydroxylic alcohols
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/78—Separation; Purification; Stabilisation; Use of additives
    • C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
    • C07C45/82—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/04—Saturated compounds containing keto groups bound to acyclic carbon atoms
    • C07C49/17—Saturated compounds containing keto groups bound to acyclic carbon atoms containing hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B61/00—Other general methods

Definitions

  • the present invention relates to a method for producing 1,3-butylene glycol (1,3-butanediol).
  • 1,3-butylene glycol is a viscous, colorless, transparent, odorless liquid having a boiling point of 208 ° C., has excellent solubility, and produces a derivative with excellent chemical stability. It is used as a raw material for various synthetic resins and surfactants, and as a raw material for cosmetics, hygroscopic agents, high-boiling solvents, and antifreeze liquids because of its excellent hygroscopic properties, low volatility, and low toxicity. Yes.
  • non-toxic and non-irritating 1,3-butylene glycol has excellent properties as a moisturizing agent in the cosmetic industry, and its demand has greatly increased. Odorless 1,3-butylene glycol is useful as a cosmetic grade. is there.
  • Examples of the industrial production method of 1,3-butylene glycol include the following four methods (I) to (IV).
  • (I) A method in which 1,3-butylene glycol is obtained by subjecting acetaldehyde to aldol condensation to obtain acetaldols and catalytic reduction thereof.
  • (II) A method for obtaining 1,3-butylene glycol by hydrolysis of 1,3-butylene oxide.
  • (III) A method for obtaining 1,3-butylene glycol from propylene and formaldehyde using the Prince reaction.
  • (IV) A method of obtaining 1,3-butylene glycol by hydrogenating 4-hydroxy-2-butanone.
  • the method (II) is not a practical method because an industrial method has not yet been established. Further, the method (III) has been found to have a low yield, and is not a practical method. Therefore, in general, 1,3-butylene glycol is produced by the method (I), but the intermediate acetoaldol is a structurally unstable substance, and is easily dehydrated and poisonous. There is a problem of producing crotonaldehyde. In the catalytic reduction step, for example, butanol or 2-butanone is by-produced. These impurities are difficult to separate in the purification process of 1,3-butylene glycol by distillation or the like, and adversely affect the quality and odor of products especially for cosmetics.
  • 1,3-butylene glycol obtained by this method is difficult to store for a long period of time because a slight odor is generated due to a change over time during long-term storage. Therefore, it is desired to supply 1,3-butylene glycol which has no odor component and does not have a slight odor even after long-term storage.
  • Patent Document 2 discloses a distillation by adding a compound such as caustic soda when performing distillation for removing high-boiling substances. The method of doing is disclosed.
  • Patent Document 3 discloses that after adding an alkali metal base to a crude 1,3-butylene glycol excluding high-boiling substances and heat-treating it, 1,3-butylene glycol is distilled off to obtain an alkali metal compound and a high-boiling compound.
  • Disclosed is a method in which the boilers are separated as a residue, and subsequently low boilers are distilled off from the 1,3-butylene glycol fraction.
  • Patent Document 4 discloses a method of bringing crude 1,3-butylene glycol into contact with a nonionic porous resin.
  • 1,3-butylene glycol obtained by any of the above methods is produced by aldol condensation of acetaldehyde, there is a concern that a slight odor is generated due to a change with time during long-term storage.
  • Patent Document 5 uses a microorganism
  • Patent Document 6 uses an optically active hydrogenation catalyst to obtain optically active 1,3-butylene glycol. Is disclosed.
  • Examples of the method for producing 1,3-butylene glycol from 4-hydroxy-2-butanone include the methods disclosed in Patent Documents 5 and 6 above.
  • the method disclosed in Patent Document 5 is an advantageous method for obtaining optically active 1,3-butylene glycol, focusing on a method for asymmetric reduction of microorganisms, and a method that requires the use of microorganisms. It is.
  • the method disclosed in Patent Document 6 is a method using an expensive catalyst advantageous for obtaining optically active 1,3-butylene glycol, specifically, a complex catalyst containing an optically active ligand. It is.
  • the methods disclosed in these documents are suitable for producing optically active 1,3-butylene glycol, and as a method for producing 1,3-butylene glycol that does not need to be optically active, It was not an economically advantageous method.
  • an object of the present invention is to provide a method for producing 1,3-butylene glycol industrially at low cost.
  • 1,3-butylene glycol is obtained by hydrogenating 4-hydroxy-2-butanone using a metal catalyst supported on a support, which is used industrially.
  • the present invention includes the following items. [1] comprising a step of hydrogenating 4-hydroxy-2-butanone, A method for producing 1,3-butylene glycol, which uses a metal catalyst supported on a support in the above step. [2] The method for producing 1,3-butylene glycol according to [1], wherein the metal catalyst includes at least one selected from the group consisting of platinum, palladium, cobalt, ruthenium, and rhodium. [3] The method for producing 1,3-butylene glycol according to [1] or [2], wherein the carrier comprises alumina. [4] The method according to any one of [1] to [3], including a step of purifying 4-hydroxy-2-butanone by distillation under reduced pressure at 3.0 kPa or less before the hydrogenation reaction step. Of 1,3-butylene glycol.
  • 1,3-butylene glycol can be obtained with a high yield, it is possible to provide a method for producing 1,3-butylene glycol at an industrially low cost.
  • the method for producing 1,3-butylene glycol according to an embodiment of the present invention includes a step of hydrogenating 4-hydroxy-2-butanone, and using the metal catalyst supported on the support in the above step, This is a method for producing 3-butylene glycol.
  • the hydrogenation reaction refers to a reaction for reducing a compound by reacting with hydrogen.
  • 1,3-butylene glycol obtained by hydrogenation of 4-hydroxy-2-butanone is a by-product that is more irritating and toxic than 1,3-butylene glycol synthesized from acetaldehyde. Therefore, the odor after long-term storage of 1,3-butylene glycol can be expected to be reduced.
  • 4-Hydroxy-2-butanone (hereinafter also referred to as “substrate”) used as a raw material is not particularly limited, and a commercially available product can be used. Although it may be unpurified, from the viewpoint of improving the yield of 1,3-butylene glycol, a step of performing purification treatment by dehydration, washing, distillation, adsorption, ion exchange, membrane separation, or a combination thereof It is also possible to use a material from which impurities have been removed through the process. In particular, it is preferable to use distillation as a purification treatment method from the viewpoint of reducing production costs and obtaining high-purity 1,3-butylene glycol.
  • the distillation method is not particularly limited as long as it is a distillation method that can separate low-boiling products, high-boiling products, salt content, and the like from 4-hydroxy-2-butanone obtained by utilizing the difference in boiling points.
  • Various methods such as decompression, normal pressure, pressurization, azeotropy, extraction, and reaction can be used.
  • distillation under reduced pressure (3.0 kPa or less) at a high vacuum is preferable.
  • the distillation temperature is usually 10 ° C.
  • the purity of 4-hydroxy-2-butanone is not particularly limited, but is preferably 80% or more, more preferably 90% or more, from the viewpoint of improving the yield of 1,3-butylene glycol, and 95 % Or more is more preferable, and 98% or more is particularly preferable.
  • Purity can be improved by applying the various purification methods described above to remove impurities.
  • the purity can be measured by gas chromatography. For example, a GC-2025 gas chromatograph manufactured by Shimadzu Corporation can be used.
  • the hydrogen used for the hydrogenation reaction is not particularly limited, and those usually used for the hydrogenation reaction of chemical synthesis can be used.
  • the purity of hydrogen is not particularly limited, but is preferably 99% or more, particularly preferably 99.999% or more, from the viewpoint of improving reaction efficiency.
  • the purity of hydrogen can be changed by selecting a commercial grade.
  • a metal catalyst supported on a support (hereinafter also simply referred to as “catalyst”) is used from the viewpoint of improving reaction efficiency.
  • the type of the metal catalyst is not particularly limited, and includes, for example, platinum, palladium, cobalt, ruthenium, rhodium and the like from the viewpoint of improving reaction efficiency, and includes at least one selected from the group consisting of these options. It is preferable. Of these options, platinum, palladium, cobalt, and rhodium are preferred.
  • These metal catalysts may be used alone or in combination of two or more metals in any combination and ratio. These metal catalysts are particularly advantageous when a catalytic hydrogenation method is adopted as the hydrogenation reaction.
  • the amount of the metal catalyst is not particularly limited.
  • the amount of 4-hydroxy-2-butanone when the amount of 4-hydroxy-2-butanone is 100% by weight, usually 0.1 to 20% by weight. %, Preferably 1 to 10% by weight, more preferably 1 to 5% by weight.
  • the amount of 4-hydroxy-2-butanone and the catalyst is changed every time 10% of the total time of the reaction process elapses.
  • the amount of 4-hydroxy-2-butanone and the catalyst can be measured and calculated as the average value of the amounts measured several times.
  • the usage mode of a metal catalyst is not specifically limited, it can be used by suspending or filling, and it is preferable to use it by suspending from the viewpoint of improving reaction efficiency.
  • the packing method is, for example, a method using a continuous apparatus in which a catalyst is packed and fixed in a vertically long apparatus called “reaction tower” or “packed tower”, a substrate is flowed from the top to the bottom, and hydrogen is charged from the bottom. Is mentioned.
  • the type of the carrier that supports the metal catalyst is not particularly limited, and examples thereof include metal compounds, inorganic oxides, inorganic materials, and organic materials, but include metal compounds from the viewpoint of improving reaction efficiency. It is preferable.
  • the metal compound include alumina, diatomaceous earth, silica gel, silica alumina, activated carbon and the like from the viewpoint of versatility, and alumina is particularly preferable.
  • the shape of the carrier is not particularly limited, and examples thereof include powder, granule, and molding. From the viewpoint of reactivity, a powder is preferable. Moreover, a pore structure, a crystal structure, etc. may be sufficient.
  • the amount of the metal catalyst relative to the total of the metal catalyst and the carrier supporting the metal catalyst is usually 0.1% by weight or more, more preferably 1% by weight or more, from the viewpoint of improving reaction efficiency. From the viewpoint of catalyst cost, it is usually 10% by weight or less, and more preferably 5% by weight or less.
  • the method of hydrogenation reaction is not particularly limited, and a conventional method using a reduction reaction of a carbonyl compound with a reducing agent can be used.
  • a catalytic hydrogenation method using hydrogen as a reducing agent or a hydrogenation reducing agent is used.
  • the catalytic hydrogenation method is preferable from the economical viewpoint such as reduction in production cost.
  • the hydrogenation reaction may be performed in the presence of a solvent.
  • Solvents that can be used are not particularly limited as long as they are inert to the reduction reaction, and include, for example, hydrocarbons, carboxylic acids, ethers, esters, amides, etc. Since high hydrogen pressure is not required, it is not necessary to use it.
  • the atmosphere in the system before the hydrogenation reaction is preferably filled with an inert gas. Nitrogen, argon, etc. can be used as this inert gas, and it is preferable that it is nitrogen from a viewpoint of manufacturing cost reduction.
  • the inert gas is completely replaced with hydrogen.
  • the reaction atmosphere of the hydrogenation reaction is not particularly limited, but it is preferable to use an inert gas.
  • the inert gas for example, nitrogen or argon can be used, and nitrogen is preferable from the viewpoint of reducing the manufacturing cost.
  • the reaction temperature of the hydrogenation reaction is not particularly limited, but is usually ⁇ 20 ° C. to 200 ° C., preferably 20 ° C. to 80 ° C. from the viewpoint of aging and promoting stable reaction. The temperature is preferably 40 to 60 ° C.
  • the hydrogen pressure of the hydrogenation reaction is not particularly limited, but is usually 0.1 to 20 MPa, preferably 0.1 to 10 MPa, more preferably 0 from the viewpoint of promoting a stable reaction over time. .1 to 2.0 MPa.
  • the reaction is slower when a solvent is not used than when a solvent is used, and a hydrogenation reaction at a relatively low hydrogen pressure is possible.
  • the reaction time of the hydrogenation reaction is not particularly limited, but is usually 1 to 10 hours, preferably 2 to 8 hours, and more preferably 3 to 6 hours from the viewpoint of reducing production costs.
  • the method for hydrogenating 4-hydroxy-2-butanone is not particularly limited, and a generally known method can be used.
  • steps other than the above-mentioned step of hydrogenating 4-hydroxy-2-butanone and the step of purifying the raw material liquid containing 4-hydroxy-2-butanone examples include a step of preparing a raw material liquid by mixing 4-hydroxy-2-butanone and a metal catalyst, a step of supplying the raw material liquid to the reactor, and a step of discharging the reaction liquid from the reactor.
  • the reaction can be carried out by any of batch, semi-batch, and continuous methods, but from the viewpoint of reducing production costs, it is preferable to carry out the reaction in a continuous manner.
  • the reaction solution subjected to the hydrogenation reaction is preferably subjected to a filtration step using a pressure filter or the like.
  • the unfiltered reaction crude liquid and / or the reaction crude liquid obtained by filtration are free from 1,3-butylene glycol having a high purity except for unreacted raw materials and by-products in the reaction, and / or moisture.
  • a purification step As a purification method in the above purification step, a method using dehydration, washing, distillation, adsorption, ion exchange, membrane separation, a combination thereof, or the like may be used. In particular, from the viewpoint of economy, it is preferable to use distillation as a purification method.
  • the distillation method is not particularly limited as long as it is a distillation method that can separate low-boiling products, high-boiling products, salt, etc. from 1,3-butylene glycol obtained by utilizing the difference in boiling points.
  • Various methods such as normal pressure, pressurization, azeotropy, extraction, and reaction can be used.
  • the distillation temperature is usually 20 ° C. or higher, usually 200 ° C. or lower, preferably 150 ° C. or lower, and preferably 100 ° C. or lower from the viewpoint of suppressing side reactions. It is more preferable.
  • the conversion rate from 4-hydroxy-2-butanone and the selectivity of 1,3-butylene glycol are both higher in the hydrogenation reaction.
  • the conversion rate from 4-hydroxy-2-butanone is defined as “(raw material 4-hydroxy-2-butanone (mol))-(after reaction, unreacted 4-hydroxyl contained in the reaction liquid. -2-butanone (mol)) / (raw material 4-hydroxy-2-butanone (mol)) ⁇ 100 (mol%) ”.
  • the selectivity of 1,3-butylene glycol is “(1,3-butylene glycol (mol) contained in the reaction solution after the reaction) / ((4-hydroxy-2-y of raw material).
  • the method for measuring these molar amounts is not particularly limited, but can be measured using gas chromatography as described in the Examples below.
  • the present invention will be described in more detail with reference to examples.
  • the present invention is not limited to the following examples unless it exceeds the gist.
  • the various conditions in the following Examples and the values of the evaluation results show the preferable range of the present invention as well as the preferable range in the embodiment of the present invention.
  • the preferable range of the present invention is in the above-described embodiment. It can be determined in consideration of a preferable range and a range indicated by a combination of values of the following examples or values of the examples.
  • the filtrate was distilled and separated using a 30-stage Oldershaw to obtain 1,3-butylene glycol.
  • the conversion rate from 4-hydroxy-2-butanone was 98.2%, and the selectivity for 1,3-butylene glycol was 96.0%.
  • 1,3-butylene glycol obtained by distillation was analyzed by GC, crotonaldehyde and methyl vinyl ketone were not detected.
  • Example 2 In a 1500 mL autoclave reactor, 1000 g of 4-hydroxy-2-butanone (purity 98%) distilled under reduced pressure (3.0 kPa or less, distillation temperature 80 ° C. or less) at a high degree of vacuum was added, and 100 g of 5 wt% Ru / alumina was added. The system is replaced with nitrogen. Thereafter, hydrogen gas is charged, the temperature is raised to 50 ° C., and the reaction is performed for 4 hours while maintaining the hydrogen pressure at 0.8 MPa. After the reaction, the lid of the autoclave was opened, the entire reaction solution was filtered with a pressure filter, and the filtrate was subjected to GC analysis.
  • the filtrate was distilled and separated using a 30-stage Oldershaw to obtain 1,3-butylene glycol.
  • the conversion rate from 4-hydroxy-2-butanone was 56.3%, and the selectivity for 1,3-butylene glycol was 92.0%.
  • 1,3-butylene glycol obtained by distillation was analyzed by GC, crotonaldehyde and methyl vinyl ketone were not detected.
  • the 1,3-butylene glycol obtained by the present invention can be used as a cosmetic material by utilizing synthetic resin, surfactant, hygroscopic agent, high boiling point solvent, antifreeze, especially hygroscopic, low volatility, or low toxicity. Useful.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention concerne un procédé de production de 1,3-butylène glycol, le procédé comprenant une étape d'hydrogénation de 4-hydroxy-2-butanone, et impliquant l'utilisation d'un catalyseur métallique supporté sur un support dans l'étape susmentionnée. Dans l'étape susmentionnée, le catalyseur métallique comprend de préférence au moins un élément choisi dans le groupe constitué par le platine, le palladium, le cobalt, le ruthénium et le rhodium, et le support comprend de préférence de l'alumine.
PCT/JP2019/022563 2018-06-12 2019-06-06 Procédé de production de 1,3-butylène glycol WO2019240009A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114890867A (zh) * 2022-05-30 2022-08-12 万华化学集团股份有限公司 一种制备1,3-丁二醇的方法
JPWO2023033099A1 (fr) * 2021-09-02 2023-03-09
JPWO2023058687A1 (fr) * 2021-10-06 2023-04-13
WO2023228448A1 (fr) * 2022-05-23 2023-11-30 Ｋｈネオケム株式会社 Produit de 1,3-butylène glycol

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB853266A (en) * 1956-02-24 1960-11-02 Celanese Corp 1,3-butylene glycol
JP2008504260A (ja) * 2004-06-25 2008-02-14 イーストマン ケミカル カンパニー ホスフィン−アミノホスフィン配位子のルテニウム錯体
WO2014077130A1 (fr) * 2012-11-13 2014-05-22 株式会社ダイセル Procédés de fabrication de 3-hydroxytétrahydrofuranne et de 1,3-butanediol
JP2017523238A (ja) * 2014-07-23 2017-08-17 フンダシオン テクナリア リサーチ アンド イノベーション ２，３−ブタンジオールを製造するための方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB853266A (en) * 1956-02-24 1960-11-02 Celanese Corp 1,3-butylene glycol
JP2008504260A (ja) * 2004-06-25 2008-02-14 イーストマン ケミカル カンパニー ホスフィン−アミノホスフィン配位子のルテニウム錯体
WO2014077130A1 (fr) * 2012-11-13 2014-05-22 株式会社ダイセル Procédés de fabrication de 3-hydroxytétrahydrofuranne et de 1,3-butanediol
JP2017523238A (ja) * 2014-07-23 2017-08-17 フンダシオン テクナリア リサーチ アンド イノベーション ２，３−ブタンジオールを製造するための方法

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2023033099A1 (fr) * 2021-09-02 2023-03-09
JP7335461B2 (ja) 2021-09-02 2023-08-29 Ｋｈネオケム株式会社 製品１，３－ブチレングリコールの製造方法
JPWO2023058687A1 (fr) * 2021-10-06 2023-04-13
WO2023058687A1 (fr) * 2021-10-06 2023-04-13 Ｋｈネオケム株式会社 Procédé de production de 1,3-butylène glycol de pureté élevée
JP7366295B2 (ja) 2021-10-06 2023-10-20 Ｋｈネオケム株式会社 高純度１，３－ブチレングリコールの製造方法
JP7408005B1 (ja) 2021-10-06 2024-01-04 Ｋｈネオケム株式会社 高純度１，３－ブチレングリコールの製造方法
WO2023228448A1 (fr) * 2022-05-23 2023-11-30 Ｋｈネオケム株式会社 Produit de 1,3-butylène glycol
CN114890867A (zh) * 2022-05-30 2022-08-12 万华化学集团股份有限公司 一种制备1,3-丁二醇的方法
CN114890867B (zh) * 2022-05-30 2023-03-28 万华化学集团股份有限公司 一种制备1,3-丁二醇的方法

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