JP2016526546A - Method for producing 1,3-butanediol - Google Patents

Method for producing 1,3-butanediol Download PDF

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JP2016526546A
JP2016526546A JP2016522454A JP2016522454A JP2016526546A JP 2016526546 A JP2016526546 A JP 2016526546A JP 2016522454 A JP2016522454 A JP 2016522454A JP 2016522454 A JP2016522454 A JP 2016522454A JP 2016526546 A JP2016526546 A JP 2016526546A
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acetaldehyde
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アイゼナッハー・マティアス
シュトルッツ・ハインツ
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オクセア・ゲゼルシャフト・ミト・べシュレンクテル・ハフツング
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    • 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
    • C07C29/147—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 carboxylic acids or derivatives thereof
    • C07C29/149—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 carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
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    • C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
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    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
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    • C07C51/12—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on an oxygen-containing group in organic compounds, e.g. alcohols

Abstract

本発明は、Ｃ１構成ブロックとしてのメタノールから出発した１，３−ブタンジオールの合成に関する。メタノールはアセトアルデヒドに転化され、これは二量体化され、次いで還元される。The present invention relates to the synthesis of 1,3-butanediol starting from methanol as the C1 building block. Methanol is converted to acetaldehyde, which is dimerized and then reduced.

Description

本発明は、１，３−ブタンジオールの製造方法に関する。   The present invention relates to a method for producing 1,3-butanediol.

１，３−ブタンジオールは重要な工業製品である。これは、高沸点溶剤として、凍結保護剤として、あるいは可塑剤またはフィルム結合助剤（Ｆｉｌｍｂｉｎｄｅｈｉｌｆｓｍｉｔｔｅｌ）として並びにポリエステルとして使用されるエステル化合物の製造のためのジオールとして役立つ。工業分野での使用の他、１，３−ブタンジオールは、動物飼料添加物としてまたは化粧料調合物の製造のためにも加工される。   1,3-butanediol is an important industrial product. This serves as a diol for the production of ester compounds used as high boiling solvents, as cryoprotectants, or as plasticizers or film binding aids as well as polyesters. Besides use in the industrial field, 1,3-butanediol is also processed as an animal feed additive or for the production of cosmetic formulations.

１，３−ブタンジオールの合成のための方法は通常はエチレンなどのＣ２原料から出発し、これを次いで二量体化反応を介して１，３−ブタンジオールに変換する。   The process for the synthesis of 1,3-butanediol usually starts with a C2 feed such as ethylene, which is then converted to 1,3-butanediol via a dimerization reaction.

ＷＯ２０１００１４１４６Ａ２WO2010014146A2 ＷＯ２０１１／０５６５９５WO2011 / 056595 ＷＯ２０１１／０５６５９７WO2011 / 056597 ＵＳ４，３２０，３２０US 4,320,320 ＷＯ２００５／０６４０８WO2005 / 06408

“Ｕｌｌｍａｎｎｓ Ｅｎｃｙｃｌｏｐｅｄｉａ ｏｆ Ｉｎｄｕｓｔｒｉａｌ Ｃｈｅｍｉｓｔｒｙ”，Ｗｉｌｅｙ−ＶＣＨ，６ｔｈ ｅｄ．２００３，Ｖｏｌ．１，ｐｐ．１５１−１６５“Ullmanns Encyclopedia of Industrial Chemistry”, Wiley-VCH, 6th ed. 2003, Vol. 1, pp. 151-165 Ａｒｐｅ “Ｉｎｄｕｓｔｒｉｅｌｌｅ Ｏｒｇａｎｉｓｃｈｅ Ｃｈｅｍｉｅ”，Ｗｉｌｅｙ−ＶＣＨ，６ｔｈ ｅｄ．ｐ．１９８Arpe “Industrielle Organische Chemie”, Wiley-VCH, 6th ed. p. 198 “Ｕｌｌｍａｎｎｓ Ｅｎｃｙｃｌｏｐｅｄｉａ ｏｆ Ｉｎｄｕｓｔｒｉａｌ Ｃｈｅｍｉｓｔｒｙ”，Ｗｉｌｅｙ−ＶＣＨ，６ｔｈ ｅｄ．２００３，Ｖｏｌ．１，ｐｐ．１３５−１３６“Ullmanns Encyclopedia of Industrial Chemistry”, Wiley-VCH, 6th ed. 2003, Vol. 1, pp. 135-136 “Ｕｌｌｍａｎｎｓ Ｅｎｃｙｃｌｏｐｅｄｉａ ｏｆ Ｉｎｄｕｓｔｒｉａｌ Ｃｈｅｍｉｓｔｒｙ”，Ｗｉｌｅｙ−ＶＣＨ，６ｔｈ ｅｄ．２００３，Ｖｏｌ．１２，ｐｐ．４０４−４０５“Ullmanns Encyclopedia of Industrial Chemistry”, Wiley-VCH, 6th ed. 2003, Vol. 12, pp. 404-405 Ａｒｐｅ “Ｉｎｄｕｓｔｒｉｅｌｌｅ Ｏｒｇａｎｉｓｃｈｅ Ｃｈｅｍｉｅ”，Ｗｉｌｅｙ−ＶＣＨ，６ｔｈ ｅｄ．ｐｐ．２０２−２０３Arpe “Industrielle Organische Chemie”, Wiley-VCH, 6th ed. pp. 202-203 Ｋｉｒｋ−Ｏｔｈｍｅｒ，Ｅｎｃｙｃｌｏｐｅｄｉａ ｏｆ Ｃｈｅｍｉｃａｌ Ｔｅｃｈｎｏｌｏｇｙ，３ｒｄ Ｅｄ．Ｗｉｌｅｙ−Ｉｎｔｅｒｓｃｉｅｎｃｅｓ，Ｎｅｗ Ｙｏｒｋ，１９８０Kirk-Othmer, Encyclopedia of Chemical Technology, 3rd Ed. Wiley-Intersciences, New York, 1980

しかし、１，３−ブタンジオールの重要性のために、代替的な合成戦略及び経路についての絶え間ない要望が存在する。   However, due to the importance of 1,3-butanediol, there is a constant need for alternative synthetic strategies and routes.

それ故、１，３−ブタンジオールの新しい合成経路を提供とするというのが本発明の課題である。この課題は、本発明の合成方法によって解決される。それによれば、次のステップ、すなわち
ａ）メタノールから出発してアセトアルデヒドを合成するステップ、
ｂ）アセトアルデヒドを二量体化してアセトアルドールとするステップ、及び
ｃ）アセトアルドールを還元して１，３−ブタンジオールとするステップ、
を含む合成方法が提案される。 Therefore, it is an object of the present invention to provide a new synthesis route for 1,3-butanediol. This problem is solved by the synthesis method of the present invention. According to it, the next step, a) synthesizing acetaldehyde starting from methanol,
b) dimerizing acetaldehyde to acetaldol, and c) reducing acetoaldol to 1,3-butanediol,
A synthesis method including is proposed.

それ故、上記合成方法によって、メタノールなどの入手し易いＣ１構成ブロックから出発した１，３−ブタンジオールの合成が可能となる。本発明による方法は、多くの用途において、特に、次の利点の一つまたは二つ以上を供する。
−アセトアルデヒドを二つのＣ１構成ブロック（この際、構成ブロックの一つはメタノールである）の反応により合成することによって、エチレンの使用を避けることができる。原料としてのメタノールは、天然ガス、石炭またはバイオマスなどの様々な原料源に基づいて多量に安価に入手でき、そして常圧及び室温下に液状の化合物として簡単に輸送できる。
−慣用の方法に従う酸化によるエチレンからのアセトアルデヒドの製造は、非常に煩雑で、特別な原材料を必要とし、そして廃棄物処理に関して生態学的にかなり問題がある。 Therefore, the above synthesis method allows the synthesis of 1,3-butanediol starting from readily available C1 building blocks such as methanol. The method according to the invention offers one or more of the following advantages in many applications, in particular:
- two C 1 building block (this time, one building block is methanol) acetaldehyde by synthesized by reacting, avoids the use of ethylene. Methanol as a raw material is available in large quantities at low cost based on various raw material sources such as natural gas, coal or biomass, and can be easily transported as a liquid compound at normal pressure and room temperature.
The production of acetaldehyde from ethylene by oxidation according to conventional methods is very cumbersome, requires special raw materials and is quite ecologically problematic with regard to waste disposal.

該方法の個々のステップを以下に説明する。   The individual steps of the method are described below.

ステップａ）アセトアルデヒド合成：
このアセトアルデヒド合成は様々な経路で行うことができ、それ故、これらは全て本発明の好ましい形態である。 Step a) Acetaldehyde synthesis:
This acetaldehyde synthesis can be carried out by various routes, and therefore they are all preferred forms of the present invention.

１）メタノールから酢酸への反応による合成：
第一の好ましい実施形態の一つでは、先ずメタノールを合成ガスにより酢酸に転化する。可能な転化方法の一つは、中でも、“Ｕｌｌｍａｎｎｓ Ｅｎｃｙｃｌｏｐｅｄｉａ ｏｆ Ｉｎｄｕｓｔｒｉａｌ Ｃｈｅｍｉｓｔｒｙ”，Ｗｉｌｅｙ−ＶＣＨ，６ｔｈ ｅｄ．２００３，Ｖｏｌ．１，ｐｐ．１５１−１６５（非特許文献１）に記載されている。この場合、メタノールを、ロジウムまたはイリジウム触媒の存在下に一酸化炭素でカルボニル化する。 1) Synthesis by reaction from methanol to acetic acid:
In one first preferred embodiment, methanol is first converted to acetic acid with synthesis gas. One possible conversion method is, among others, “Ullmanns Encyclopedia of Industrial Chemistry”, Wiley-VCH, 6th ed. 2003, Vol. 1, pp. 151-165 (Non-Patent Document 1). In this case, methanol is carbonylated with carbon monoxide in the presence of rhodium or iridium catalyst.

こうして得られた酢酸は直接アセトアルデヒドに還元できる。対応する好ましい手順は、中でも、ＷＯ２０１００１４１４６Ａ２（特許文献１）に論じられている。   The acetic acid thus obtained can be reduced directly to acetaldehyde. Corresponding preferred procedures are discussed, inter alia, in WO20110014146A2.

代替的に、酢酸は、中間段階としてのエタノールを介してアセトアルデヒドに転化することができる。   Alternatively, acetic acid can be converted to acetaldehyde via ethanol as an intermediate step.

この際、このエタノール合成は、例えばＡｒｐｅ“Ｉｎｄｕｓｔｒｉｅｌｌｅ Ｏｒｇａｎｉｓｃｈｅ Ｃｈｅｍｉｅ”，Ｗｉｌｅｙ−ＶＣＨ，６ｔｈ ｅｄ．ｐ．１９８（非特許文献２）に従い、先ず酢酸を更なるメタノールと反応させてメチルアセテートとし、これを、気相水素分解により、エタノール及びメタノールに分裂することによって行うことができ； 得られたメタノールは、当然、新たなエステル化にまたは酢酸合成のいずれかに送還することができる。   In this case, this ethanol synthesis is carried out by, for example, Arpe “Industrielle Organische Chemie”, Wiley-VCH, 6th ed. p. According to 198 (Non-Patent Document 2), acetic acid is first reacted with further methanol to give methyl acetate, which can be obtained by splitting into ethanol and methanol by gas phase hydrogenolysis; Of course, it can be sent back to either new esterification or to acetic acid synthesis.

代替的に、例えばＷＯ２０１１／０５６５９５（特許文献２）またはＷＯ２０１１／０５６５９７（特許文献３）に従い、酢酸を、高められた温度（１２５〜３５０℃）及び圧力（１０〜３０００ｋＰａ）下に、水素及び適切な触媒を用いてエタノールに水素化することができる。   Alternatively, acetic acid is treated with hydrogen and an appropriate amount under elevated temperature (125-350 ° C.) and pressure (10-3000 kPa), for example according to WO 2011/056595 (Patent Document 2) or WO 2011/056597 (Patent Document 3). Can be hydrogenated to ethanol using any suitable catalyst.

エタノールの酸化は、好ましくは、５００〜６５０℃で銀触媒上にエタノール−空気混合物を導通してまたは２６０〜２９０℃下に促進銅触媒上で気相中で脱水素化して行われる。このためには、例えば“Ｕｌｌｍａｎｎｓ Ｅｎｃｙｃｌｏｐｅｄｉａ ｏｆ Ｉｎｄｕｓｔｒｉａｌ Ｃｈｅｍｉｓｔｒｙ”，Ｗｉｌｅｙ−ＶＣＨ，６ｔｈ ｅｄ．２００３，Ｖｏｌ．１，ｐｐ．１３５−１３６（非特許文献３）を参照されたい。   The oxidation of ethanol is preferably carried out by passing an ethanol-air mixture over the silver catalyst at 500-650 ° C. or dehydrogenating in the gas phase over a promoted copper catalyst at 260-290 ° C. For this purpose, for example, “Ullmanns Encyclopedia of Industrial Chemistry”, Wiley-VCH, 6th ed. 2003, Vol. 1, pp. 135-136 (Non-Patent Document 3).

２）メタノールのホモロゲーションによる合成：
代替的に、メタノールをＣＯ／Ｈ２を用いてホモログ化してエタノールとすることができる。このためには、中でも“Ｕｌｌｍａｎｎｓ Ｅｎｃｙｃｌｏｐｅｄｉａ ｏｆ Ｉｎｄｕｓｔｒｉａｌ Ｃｈｅｍｉｓｔｒｙ”，Ｗｉｌｅｙ−ＶＣＨ，６ｔｈ ｅｄ．２００３，Ｖｏｌ．１２，ｐｐ．４０４−４０５（非特許文献４）及び／またはＵＳ４，３２０，３２０（特許文献４）に記載のように、鉄コバルトカルボニルが、ヨウ化物促進剤の添加下に１００〜２５０℃の温度及び５〜１００ＭＰａの圧力において有効である。 2) Synthesis by methanol homologation:
Alternatively, methanol can be homologated with CO / H 2 to ethanol. To this end, among other things, “Ullmanns Encyclopedia of Industrial Chemistry”, Wiley-VCH, 6th ed. 2003, Vol. 12, pp. As described in 404-405 (Non-patent Document 4) and / or US 4,320,320 (Patent Document 4), iron cobalt carbonyl is added at a temperature of 100-250 ° C. and 5- Effective at a pressure of 100 MPa.

こうして得られたエタノールは、次いで上述のようにアセトアルデヒドに転化することができる。   The ethanol thus obtained can then be converted to acetaldehyde as described above.

３）メタノールからアセトアルデヒドへの直接転化による合成
上記のメタノールホモロゲーションは、（変化させた反応条件、特に変化させたＣＯ／Ｈ２比、温度及び／または圧力下に）アセトアルデヒドの直接的な合成にも利用できる。 3) Synthesis by direct conversion of methanol to acetaldehyde The methanol homologation described above is a direct synthesis of acetaldehyde (under altered reaction conditions, especially under altered CO / H 2 ratio, temperature and / or pressure). Can also be used.

ｂ）アセトアルドールへの二量体化
ステップａ）で得られたアセトアルデヒドを今度はアルドール反応を用いて二量体化してアセトアルドールとする。この際、アルドール反応は、好ましくは水性アルカリ溶液中で行われる。多くの用途において、反応を完全な転化率まで行わずに、転化率が約５０〜６０％のところで中断することが有利であることが判明した。なぜならば、そうすることで、副生成物の生成を避けることができるかまたは少なくとも減らすことができるからである。これに関しては、中でも、Ａｒｐｅ“Ｉｎｄｕｓｔｒｉｅｌｌｅ Ｏｒｇａｎｉｓｃｈｅ Ｃｈｅｍｉｅ”，Ｗｉｌｅｙ−ＶＣＨ，６ｔｈ ｅｄ．ｐｐ．２０２−２０３（非特許文献５）を参照されたい。 b) Dimerization to acetaldol The acetaldehyde obtained in step a) is then dimerized using an aldol reaction to acetaldol. In this case, the aldol reaction is preferably carried out in an aqueous alkaline solution. In many applications, it has been found advantageous to interrupt the reaction at about 50-60% without carrying out the reaction to full conversion. This is because by doing so, the production of by-products can be avoided or at least reduced. In this regard, among others, Arpé "Industrielle Organische Chemie", Wiley-VCH, 6th ed. pp. 202-203 (Non-Patent Document 5).

上記の中断は、最も簡単には酸の添加によって行われ； 未転化のアセトアルデヒドは、例えば蒸発させて簡単に除去することができ、次いで送還することができる。   The interruption described above is most simply performed by addition of acid; unconverted acetaldehyde can be easily removed, for example by evaporation, and then returned.

ｃ）アセトアルドールの還元
ステップｂ）で得られたアセトアルドールは今度は還元によって１，３−ブタンジオールに変えることができる。この際、多くの方法が利用でき、好ましい方法は、 例えば、中でもＫｉｒｋ−Ｏｔｈｍｅｒ，Ｅｎｃｙｃｌｏｐｅｄｉａ ｏｆ Ｃｈｅｍｉｃａｌ Ｔｅｃｈｎｏｌｏｇｙ，３ｒｄ Ｅｄ．Ｗｉｌｅｙ−Ｉｎｔｅｒｓｃｉｅｎｃｅｓ，Ｎｅｗ Ｙｏｒｋ，１９８０（非特許文献６）及び／またはＷＯ２００５／０６４０８（特許文献５）に記載さるようなラネーニッケルを用いた水素化である。 c) Reduction of acetaldol The acetaldol obtained in step b) can in turn be converted to 1,3-butanediol by reduction. In this case, many methods can be used, and preferable methods include, for example, Kirk-Othmer, Encyclopedia of Chemical Technology, 3rd Ed. Hydrogenation using Raney nickel as described in Wiley-Intersciences, New York, 1980 (Non-patent Document 6) and / or WO 2005/06408 (Patent Document 5).

上述した並びに特許請求する及び実施例において記載した本発明に従い使用するべき成分は、それらの大きさ、形態、材料選択及び技術的コンセプトにおいて何の特別な例外的な条件を受けるものではなく、そのため使用分野において既知の選択基準は制限なく使用できる。   The components to be used in accordance with the present invention as described above and in the claims and examples are not subject to any special exceptional conditions in their size, form, material selection and technical concept, and therefore Selection criteria known in the field of use can be used without limitation.

既に記載の実施形態の成分及び特徴の個々の組み合わせは例示的なものであり； これらの教示と、本明細書に含まれる他の教示との交換及び置換も、引用文献と共に、明らかに意図されるものである。当業者は、ここに記載の変形、変更及び他の態様は、本発明の趣旨及び本発明の範囲を逸脱することなく同様に起こり得ることを理解するものである。   The individual combinations of components and features of the embodiments already described are exemplary; the exchange and substitution of these teachings with other teachings contained herein are also clearly contemplated, along with the cited references. Is. Those skilled in the art will appreciate that variations, modifications, and other aspects described herein can occur as well without departing from the spirit and scope of the present invention.

相応して、上記の記載は、例示的であり、限定的でないと見なされるべきである。請求項で使用している「含む」という記載は、他の成分またはステップを排除するものではない。単数表記は、複数の意味を排除するものではない。単に特定の量（Ｍａｓｓ）が互いに異なる請求項に記載されているという事実だけでは、これらの量の組み合わせが有利に使用できないことが意味されるものではない。本発明の範囲は添付の特許請求の範囲及びそれの均等方法に画定される。   Accordingly, the above description should be regarded as illustrative and not restrictive. The word “comprising” as used in the claims does not exclude other ingredients or steps. The singular does not exclude a plurality of meanings. The mere fact that certain quantities are recited in mutually different claims does not indicate that a combination of these quantities cannot be used to advantage. The scope of the present invention is defined by the appended claims and equivalents thereof.

Claims (11)

１，３−ブタンジオールの製造方法であって、次のステップ
ａ）メタノールから出発してアセトアルデヒドを合成するステップ、
ｂ）アセトアルデヒドを二量体化してアセトアルドールとするステップ、及び
ｃ）アセトアルドールを還元して１，３−ブタンジオールとするステップ、
を含む前記方法。 A method for producing 1,3-butanediol, comprising the following steps a) synthesizing acetaldehyde starting from methanol;
b) dimerizing acetaldehyde to acetaldol, and c) reducing acetoaldol to 1,3-butanediol,
Including said method. ステップａ）において、先ずメタノールをステップａ１）において酢酸に転化する、請求項１に記載の方法。 The process according to claim 1, wherein in step a), methanol is first converted into acetic acid in step a1). ステップａ１）において得られた酢酸をエタノールに還元し（ステップａ２）、次いでアセトアルデヒドに酸化する（ステップａ３）、請求項２に記載の方法。 The process according to claim 2, wherein the acetic acid obtained in step a1) is reduced to ethanol (step a2) and then oxidized to acetaldehyde (step a3). ステップａ１）において得られた酢酸をアセトアルデヒドに還元する、請求項２に記載の方法。 The process according to claim 2, wherein the acetic acid obtained in step a1) is reduced to acetaldehyde. ステップａ）において先ずメタノールをエタノールにホモログ化し、次いで得られたエタノールをアセトアルデヒドに酸化する、請求項１に記載の方法。 The process according to claim 1, wherein in step a) methanol is first homologated to ethanol and then the ethanol obtained is oxidized to acetaldehyde. メタノールをＣＯ／Ｈ２を用いて直接アセトアルデヒドに転化する、請求項１に記載の方法。 Converting methanol directly acetaldehyde with CO / H 2, The method of claim 1. ステップｂ）をアルドール反応により実施する、請求項１〜６のいずれか一つに記載の方法。 A process according to any one of the preceding claims, wherein step b) is carried out by an aldol reaction. アルドール反応を水性アルカリ溶液の使用によって行う、請求項７に記載の方法。 The process according to claim 7, wherein the aldol reaction is carried out by use of an aqueous alkaline solution. アルドール反応を転化率５０〜６０％で中断する、請求項７または８に記載の方法。 The process according to claim 7 or 8, wherein the aldol reaction is interrupted at a conversion of 50 to 60%. ステップｃ）を水素化して行う、請求項１〜９のいずれか一つに記載の方法。 The process according to any one of claims 1 to 9, wherein step c) is carried out by hydrogenation. 水素化においてラネーニッケルが触媒として使用される、請求項１０に記載の方法。 11. Process according to claim 10, wherein Raney nickel is used as catalyst in the hydrogenation.
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