JP3852972B2 - Method for producing saturated ester - Google Patents
Method for producing saturated ester Download PDFInfo
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- JP3852972B2 JP3852972B2 JP02468696A JP2468696A JP3852972B2 JP 3852972 B2 JP3852972 B2 JP 3852972B2 JP 02468696 A JP02468696 A JP 02468696A JP 2468696 A JP2468696 A JP 2468696A JP 3852972 B2 JP3852972 B2 JP 3852972B2
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は飽和エステルの製造方法であって、特定の触媒の存在下に不飽和基含有エステルを水素化することにより飽和エステルを製造する方法に関する。
【０００２】
【従来の技術】
飽和エステル類は溶剤や反応溶媒として多用され、工業上重要な化合物である。これら飽和エステル類は、一般に、飽和エステルに対応するアルコールとカルボン酸との縮合によるエステル化を介して製造される。
【０００３】
【発明が解決しようとする課題】
しかし、エステル反応系では、副生成物である水を系外に取り除かなければ、反応の平衡状態を生成側に傾けることができず、工業的に有意な原料転化率や反応速度が得られない。そのため、エステル化を介する飽和エステル類の工業的な製造は、他の反応系を介するより複雑な反応装置や反応工程を必要とし、加えて、空時収率が低く、水の蒸留分離にも多大のエネルギーを消費する等の困難を有する。
【０００４】
一方、アリル基、メタリル基等を含有する不飽和基含有エステルは、対応するオレフィンとカルボン酸との酸化的アシルオキシル化反応を介して、極めて高収率、かつ高空時収率で工業的に生産することができる。従って、容易に入手できるこれら不飽和基含有エステルに水素化反応を実行し、飽和エステルの製造を試行したところ、この反応は相当するアルカンとカルボン酸への飽和エステルの分解反応をも伴った。これを防ぎ飽和エステルを高収率で得るには、白金族金属であるロジウム（Ｒｈ）を触媒として使用することが必要となる（接触水素化反応；西村重夫他、東京化学同人、ｐ．１１７）。
しかし、白金族金属の中でもＲｈは極めて高価な金属である。Ｒｈを触媒として、飽和エステル類のごとく比較的安価な化合物を工業的に生産することは、触媒の失活がある程度不可避であることを考慮すると、経済性上の不均衡を招くことになる。
【０００５】
【課題を解決するための手段】
本発明者らは、不飽和基含有エステルの水素化反応について、鋭意検討を重ねた結果、意外にも、ラネーニッケル等の安価なニッケル系汎用水素化触媒を特定条件下で使用することにより、殆ど分解反応を伴わずに飽和エステルが高収率で得られることを見出し、本発明を完成するに至った。
【０００６】
すなわち本発明は、ニッケルを１０乃至１００重量％含有する水素化触媒を用いて、下記一般式（１）で示す不飽和基含有エステルを水素化して飽和エステルを製造する方法であって、常圧〜１０ｋｇ／ｃｍ 2 の圧力下、気相法で水素化反応を行うことを特徴とする飽和エステルの製造方法を提供するものである。また、前記不飽和基含有エステルが酢酸アリル、酢酸クロチル、酢酸メタリル、プロピオン酸アリル、プロピオン酸クロチル、プロピオン酸メタリルの群から選ばれる化合物であることを特徴とする前記飽和エステルの製造方法を提供するものである。さらに、水素化触媒が担持型ニッケルであることを特徴とする前記飽和エステルの製造方法を提供するものである。加えて、反応温度が３０乃至２００℃の範囲で水素化することを特徴とする前記飽和エステルの製造方法を提供するものである。以下、本発明について詳細に説明する。
【０００７】
【化２】
【発明の実施の形態】
本発明では、上記一般式（１）で示す不飽和基含有エステルを、飽和エステルの原料として使用することができる。ここに一般式中、Ｒ1、Ｒ2、Ｒ3、Ｒ4、Ｒ5は、炭素数１乃至１０の任意のアルキル基または水素原子を表わし、各々同一であっても異なっていてもよく、アルキル基は直鎖であっても分岐を有していてもよい。また、Ｒ6は、炭素数１乃至１０の任意のアルキル基であり、直鎖であっても分岐を有していてもよい。本発明で最も好ましく使用できるのは、Ｒ1、Ｒ2、Ｒ3、Ｒ4、Ｒ5が全て水素原子であるアリルエステル、Ｒ3がメチル基でありＲ1、Ｒ2、Ｒ4及びＲ5が全て水素原子であるクロチルエステル、Ｒ1がメチル基でありＲ2、Ｒ3、Ｒ4及びＲ5が全て水素原子であるメタリルエステルである。具体的には、酢酸アリル、プロピオン酸アリル、プロピオン酸メタリル、酢酸メタリル、プロピオン酸クロチル、酢酸クロチル等を好ましく使用することができ、特に好ましくは、酢酸アリル、酢酸クロチル、酢酸メタリルである。
【０００９】
本発明で使用する触媒は、ニッケルを主成分とする水素化触媒であり、ニッケルを１０乃至１００重量％含有する触媒が好ましく、特に好ましくはニッケル含量２０乃至９０重量％の触媒である。触媒の形態は、ニッケルを合金として含有していてもよく、担体にニッケルを担持させたものでもよい。
具体的には、ラネーニッケル等のニッケル合金や、ニッケルをシリカ、アルミナ、珪藻土などの担体に担持した担持型ニッケル触媒、さらにニッケル化合物である漆原ニッケル触媒等を例示できる。これらは、水素化用の汎用触媒として市販されているものでも使用することができる。なお、市販品は工業的規模での入手が容易である。また、市販ニッケル触媒には、触媒の活性、耐被毒性、耐熱性、耐酸性の改善等のため、ニッケル以外に助触媒として微量の他成分、例えば、Ｃｕ、Ｃｒ、Ｍｇ、Ａｌ等が添加されているものがあるが、そのような触媒であっても、本発明で好ましく使用することができる。
【００１０】
本発明における反応形態は、気相法、液相法のいずれでも可能である。気相で反応させる場合は、固定床流通反応装置の使用が最も一般的であるが、流動床装置の使用も可能である。液相で反応させる場合は、完全混合槽型、気泡塔型、トリクルベッド型等の形態で実施することができる。
【００１１】
反応温度は、原料の種類によっても異なるが、３０乃至２００℃の範囲が好ましく、５０乃至１５０℃の範囲が特に好ましい。反応温度が３０℃未満では充分な反応速度が得られず、また２００℃を超えると水素化分解が進行し、いずれも好ましくない。酢酸アリルを原料として使用する場合には５０乃至１５０℃の温度範囲であることが好ましい。
【００１２】
反応圧力は、気相反応の場合は常圧でも通常充分な活性が得られる。このため常圧で実施するのが至便である。しかし、加圧条件とすることで更に反応を加速することもできる。この場合でも、加圧条件は、１０ｋｇ／ｃｍ2以下で充分である。一方、液相反応の場合は溶解水素濃度を確保するために、通常は加圧が必要となる。この場合の反応圧力は、１０乃至１００ｋｇ／ｃｍ2の範囲であることが好ましく、特には１５乃至５０ｋｇ／ｃｍ2が好ましい。１０ｋｇ／ｃｍ2未満では、反応が十分に促進されず、一方１００ｋｇ／ｃｍ2を超えると、水素化分解が優勢となり好ましくない。
【００１３】
本発明により、酢酸ノルマルプロピル、酢酸ブチル、酢酸イソプロピル、プロピオン酸ノルマルプロピル、プロピオン酸ブチル、プロピオン酸イソプロピル等の飽和エステルを得ることができる。
【００１４】
【実施例】
以下、実施例および比較例により本発明を具体的に説明するが、本発明はこれらに限定されるものではない。なお、実施例中の転化率、選択率、収率の定義は下記式による。
【００１５】
【数１】
（実施例１）
内径１８ｍｍφのステンレス製Ｕ字型反応管に、担持型ニッケル触媒（日揮化学製「Ｎ１１１」、ニッケル含量４６重量％、円柱状成形品）６ｍｌを充填した。常圧で、水素ガスを５．６リットル／ｈｒ（ＳＴＰ値、以下同じ）で流しながら１７０℃（触媒層での最高値、以下同じ）で６時間触媒を前処理した。次いで、酢酸アリルを５．２ｇ／ｈｒ、水素ガスを５．６リットル／ｈｒで仕込みながら、１５０℃で８時間反応を継続した。
反応器出口の凝縮液をガスクロマトグラフィーにて分析した結果、酢酸アリルの転化率は９６．５％、酢酸ノルマルプロピルの選択率は９６．２％、酢酸ノルマルプロピルの収率は９２．８％であった。
【００１７】
（実施例２）
反応温度を１００℃に変更した以外は実施例１と全く同様に反応を行った。その結果、酢酸アリルの転化率は９６．５％、酢酸ノルマルプロピルの選択率は９９．１％、酢酸ノルマルプロピルの収率は９５．６％であった。
【００１８】
（実施例３）
反応温度を２３０℃に変更した以外は実施例１と全く同様に反応を行った。酢酸アリルの転化率は９８．７％、酢酸ノルマルプロピルの選択率は６６．７％、酢酸ノルマルプロピルの収率は６５．８％であった。
【００１９】
（参考例）
容量１０００ｍｌのステンレス製オートクレーブに酢酸アリルを２００ｍｌ、ラネーニッケル（アルカリ展開用処理済品：日揮化学製「Ｎ１５４」、展開前のニッケル含量５０重量％）を１０ｇ仕込み、水素ガス圧３０ｋｇ／ｃｍ2（ゲージ圧）、反応温度１００℃で攪拌しながら２時間反応させた。反応液をガスクロマトグラフィーにて分析した結果、酢酸アリルの転化率は９７．３％、酢酸ノルマルプロピルの選択率は９３．６％、酢酸ノルマルプロピルの収率は９１．１％であった。
【００２０】
【発明の効果】
本発明によれば、原料転化率、選択率、収率を高く維持しながら、飽和エステル類を工業的に製造することができる。しかも、複雑な反応装置や反応工程を必要としない。
本発明で使用する反応触媒は、通常用いられる白金族金属のロジウムと相違し、安価なニッケルを主成分とするため、容易に入手できると共に、飽和エステル類を工業的に安価に製造することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a saturated ester, which relates to a method for producing a saturated ester by hydrogenating an unsaturated group-containing ester in the presence of a specific catalyst.
[0002]
[Prior art]
Saturated esters are frequently used as solvents and reaction solvents and are industrially important compounds. These saturated esters are generally produced via esterification by condensation of an alcohol corresponding to the saturated ester and a carboxylic acid.
[0003]
[Problems to be solved by the invention]
However, in the ester reaction system, unless the by-product water is removed from the system, the equilibrium state of the reaction cannot be tilted toward the production side, and industrially significant raw material conversion and reaction rate cannot be obtained. . Therefore, industrial production of saturated esters via esterification requires more complex reactors and reaction steps via other reaction systems, and in addition, the space-time yield is low, and water is also separated by distillation. Difficult to consume a great deal of energy.
[0004]
On the other hand, unsaturated group-containing esters containing an allyl group, a methallyl group, etc. are industrially produced in an extremely high yield and a high space-time yield through an oxidative acyloxylation reaction between a corresponding olefin and a carboxylic acid. Can be produced. Therefore, hydrogenation reaction was carried out on these readily available unsaturated group-containing esters, and production of saturated esters was attempted. This reaction also involved decomposition reaction of saturated esters into the corresponding alkanes and carboxylic acids. In order to prevent this and obtain a saturated ester in a high yield, it is necessary to use a platinum group metal rhodium (Rh) as a catalyst (catalytic hydrogenation reaction; Shigeo Nishimura et al., Tokyo Chemical Dojin, p. 117). ).
However, among platinum group metals, Rh is an extremely expensive metal. Industrially producing a relatively inexpensive compound such as a saturated ester using Rh as a catalyst causes an economic imbalance, considering that the deactivation of the catalyst is inevitable to some extent.
[0005]
[Means for Solving the Problems]
As a result of intensive studies on the hydrogenation reaction of unsaturated group-containing esters, the present inventors have surprisingly found that by using an inexpensive nickel-based general-purpose hydrogenation catalyst such as Raney nickel under specific conditions, The inventors have found that a saturated ester can be obtained in high yield without a decomposition reaction, and have completed the present invention.
[0006]
That is, the present invention is a method for producing a saturated ester by hydrogenating an unsaturated group-containing ester represented by the following general formula (1) using a hydrogenation catalyst containing 10 to 100% by weight of nickel. The present invention provides a method for producing a saturated ester , wherein a hydrogenation reaction is carried out by a gas phase method under a pressure of 10 to 10 kg / cm 2 . The unsaturated ester-containing ester is a compound selected from the group consisting of allyl acetate, crotyl acetate, methallyl acetate, allyl propionate, crotyl propionate, and methallyl propionate. To do. Furthermore, the present invention provides a method for producing the saturated ester, wherein the hydrogenation catalyst is supported nickel . In addition, the present invention provides a method for producing the saturated ester, characterized in that hydrogenation is carried out at a reaction temperature in the range of 30 to 200 ° C. Hereinafter, the present invention will be described in detail.
[0007]
[Chemical 2]
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, the unsaturated group-containing ester represented by the general formula (1) can be used as a raw material for the saturated ester. Here, in the general formula, R 1 , R 2 , R 3 , R 4 , R 5 represent any alkyl group having 1 to 10 carbon atoms or a hydrogen atom, and may be the same or different, The alkyl group may be linear or branched. R 6 is an arbitrary alkyl group having 1 to 10 carbon atoms and may be linear or branched. Most preferably used in the present invention are allyl esters in which R 1 , R 2 , R 3 , R 4 and R 5 are all hydrogen atoms, R 3 is a methyl group and R 1 , R 2 , R 4 and R A crotyl ester in which 5 is a hydrogen atom, and a methallyl ester in which R 1 is a methyl group and R 2 , R 3 , R 4 and R 5 are all hydrogen atoms. Specifically, allyl acetate, allyl propionate, methallyl propionate, methallyl acetate, crotyl propionate, crotyl acetate, and the like can be preferably used, and allyl acetate, crotyl acetate, and methallyl acetate are particularly preferable.
[0009]
The catalyst used in the present invention is a hydrogenation catalyst mainly composed of nickel, preferably a catalyst containing 10 to 100% by weight of nickel, particularly preferably a catalyst having a nickel content of 20 to 90% by weight. The form of the catalyst may contain nickel as an alloy, or may be one in which nickel is supported on a carrier.
Specific examples include nickel alloys such as Raney nickel, supported nickel catalysts in which nickel is supported on a carrier such as silica, alumina, diatomaceous earth, and lacquer raw nickel catalysts that are nickel compounds. Any of those commercially available as a general-purpose catalyst for hydrogenation can be used. Commercial products are easily available on an industrial scale. In addition to nickel, a small amount of other components such as Cu, Cr, Mg, Al, etc. are added to the commercially available nickel catalyst as a co-catalyst in order to improve the activity, poisoning resistance, heat resistance, and acid resistance of the catalyst. Even such a catalyst can be preferably used in the present invention.
[0010]
The reaction form in the present invention can be either a gas phase method or a liquid phase method. When the reaction is carried out in the gas phase, the use of a fixed bed flow reactor is most common, but a fluidized bed device can also be used. When reacting in the liquid phase, it can be carried out in the form of a complete mixing tank type, bubble column type, trickle bed type or the like.
[0011]
The reaction temperature varies depending on the type of raw material, but is preferably in the range of 30 to 200 ° C, particularly preferably in the range of 50 to 150 ° C. When the reaction temperature is less than 30 ° C., a sufficient reaction rate cannot be obtained, and when it exceeds 200 ° C., hydrogenolysis proceeds, which is not preferable. When allyl acetate is used as a raw material, the temperature range is preferably 50 to 150 ° C.
[0012]
In the case of a gas phase reaction, a sufficient activity is usually obtained even at normal pressure in the case of a gas phase reaction. For this reason, it is convenient to carry out at normal pressure. However, the reaction can be further accelerated by applying pressure. Even in this case, the pressure condition is 10 kg / cm 2 or less. On the other hand, in the case of a liquid phase reaction, pressurization is usually required to ensure a dissolved hydrogen concentration. In this case, the reaction pressure is preferably in the range of 10 to 100 kg / cm 2 , particularly preferably 15 to 50 kg / cm 2 . If it is less than 10 kg / cm 2 , the reaction is not sufficiently promoted. On the other hand, if it exceeds 100 kg / cm 2 , hydrocracking becomes dominant, which is not preferable.
[0013]
According to the present invention, saturated esters such as normal propyl acetate, butyl acetate, isopropyl acetate, normal propyl propionate, butyl propionate and isopropyl propionate can be obtained.
[0014]
【Example】
EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, this invention is not limited to these. The definitions of conversion, selectivity and yield in the examples are based on the following formula.
[0015]
[Expression 1]
Example 1
A stainless steel U-shaped reaction tube having an inner diameter of 18 mmφ was filled with 6 ml of a supported nickel catalyst (“N111” manufactured by JGC Chemical Co., Ltd., nickel content: 46% by weight, cylindrical molded product). The catalyst was pretreated at 170 ° C. (maximum value in the catalyst layer, the same applies hereinafter) for 6 hours while flowing hydrogen gas at 5.6 liters / hr (STP value, the same applies hereinafter) at normal pressure. Next, the reaction was continued at 150 ° C. for 8 hours while charging allyl acetate at 5.2 g / hr and hydrogen gas at 5.6 liter / hr.
As a result of analyzing the condensate at the outlet of the reactor by gas chromatography, the conversion of allyl acetate was 96.5%, the selectivity for normal propyl acetate was 96.2%, and the yield of normal propyl acetate was 92.8%. Met.
[0017]
(Example 2)
The reaction was performed in the same manner as in Example 1 except that the reaction temperature was changed to 100 ° C. As a result, the conversion of allyl acetate was 96.5%, the selectivity for normal propyl acetate was 99.1%, and the yield of normal propyl acetate was 95.6%.
[0018]
Example 3
The reaction was performed in the same manner as in Example 1 except that the reaction temperature was changed to 230 ° C. The conversion of allyl acetate was 98.7%, the selectivity for normal propyl acetate was 66.7%, and the yield of normal propyl acetate was 65.8%.
[0019]
( Reference example )
A stainless steel autoclave with a capacity of 1000 ml is charged with 200 g of allyl acetate, 10 g of Raney nickel (treated for alkali development: “N154” manufactured by JGC Chemicals, nickel content of 50% by weight before development), hydrogen gas pressure 30 kg / cm 2 (gauge Pressure), and the reaction temperature was 100 ° C. for 2 hours with stirring. As a result of analyzing the reaction solution by gas chromatography, the conversion of allyl acetate was 97.3%, the selectivity for normal propyl acetate was 93.6%, and the yield of normal propyl acetate was 91.1%.
[0020]
【The invention's effect】
According to the present invention, saturated esters can be industrially produced while maintaining high raw material conversion, selectivity, and yield. In addition, no complicated reaction apparatus or reaction process is required.
The reaction catalyst used in the present invention is different from the commonly used platinum group metal rhodium, and since it is mainly composed of inexpensive nickel, it can be easily obtained and can produce saturated esters industrially at low cost. it can.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02468696A JP3852972B2 (en) | 1996-01-18 | 1996-01-18 | Method for producing saturated ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02468696A JP3852972B2 (en) | 1996-01-18 | 1996-01-18 | Method for producing saturated ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09194427A JPH09194427A (en) | 1997-07-29 |
| JP3852972B2 true JP3852972B2 (en) | 2006-12-06 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP02468696A Expired - Fee Related JP3852972B2 (en) | 1996-01-18 | 1996-01-18 | Method for producing saturated ester |
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| Country | Link |
|---|---|
| JP (1) | JP3852972B2 (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9823853D0 (en) * | 1998-10-30 | 1998-12-23 | Bp Chem Int Ltd | A process for making n-butyl esters from butadiene |
| AU2575800A (en) * | 1999-04-27 | 2000-11-10 | Showa Denko Kabushiki Kaisha | Process for producing hydrogenated ester, hydrogenation catalyst for use therein, and process for producing the catalyst |
| US6936730B1 (en) | 1999-04-27 | 2005-08-30 | Showa Denko K.K. | Process for producing hydrogenated ester, hydrogenating catalyst used therefor and process for producing the catalyst |
| KR100555985B1 (en) * | 1999-04-27 | 2006-03-03 | 쇼와 덴코 가부시키가이샤 | Process for producing hydrogenated ester |
| KR20010019332A (en) * | 1999-08-26 | 2001-03-15 | 김동석 | Process for preparing methyl methoxy propionate |
| US7700801B2 (en) * | 2004-11-15 | 2010-04-20 | Celanese International Corporation | Co-production of vinyl acetate and ethyl acetate |
| TWI370117B (en) | 2008-05-21 | 2012-08-11 | Showa Denko Kk | Process for producing n-propyl acetate |
| JP2011116722A (en) | 2009-12-07 | 2011-06-16 | Showa Denko Kk | METHOD FOR PRODUCING n-PROPYL ACETATE |
| JP2011136937A (en) * | 2009-12-28 | 2011-07-14 | Showa Denko Kk | MANUFACTURING METHOD OF n-PROPYL ACETATE |
| JP5608403B2 (en) * | 2010-03-31 | 2014-10-15 | 昭和電工株式会社 | Method for producing n-propyl acetate |
| WO2012098067A1 (en) * | 2011-01-19 | 2012-07-26 | Dsm Ip Assets B.V. | Preparation of 4-acetoxy-2-methylbutanal by catalytic carbon carbon double bond hydrogenation |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5249447B2 (en) * | 1972-09-11 | 1977-12-17 | ||
| JPS53127405A (en) * | 1977-04-08 | 1978-11-07 | Japan Synthetic Rubber Co Ltd | Continuous preparation of 1,4-butanediol |
| DE2928310A1 (en) * | 1979-07-13 | 1981-02-05 | Basf Ag | METHOD FOR PRODUCING BUTANEDIOL DIACETATE BY CATALYTIC HYDRATION OF BUTANEDIOL DIACETATE |
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