JP2000219649A - Production of saturated ketone compound - Google Patents
Production of saturated ketone compoundInfo
- Publication number
- JP2000219649A JP2000219649A JP11021085A JP2108599A JP2000219649A JP 2000219649 A JP2000219649 A JP 2000219649A JP 11021085 A JP11021085 A JP 11021085A JP 2108599 A JP2108599 A JP 2108599A JP 2000219649 A JP2000219649 A JP 2000219649A
- Authority
- JP
- Japan
- Prior art keywords
- ketone compound
- reaction
- unsaturated ketone
- catalyst
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明はメシチルオキシド
（ＭＯ）、ホロン（ＰＨＯ）等の不飽和ケトン化合物を
水添してメチルイソブチルケトン（ＭＩＢＫ）、ジイソ
ブチルケトン（ＤＩＢＫ）等の飽和ケトン化合物を製造
する方法に関する。The present invention relates to a method for hydrogenating an unsaturated ketone compound such as mesityl oxide (MO) or phorone (PHO) to obtain a saturated ketone compound such as methyl isobutyl ketone (MIBK) or diisobutyl ketone (DIBK). It relates to a method of manufacturing.
【０００２】[0002]
【従来の技術】ＭＩＢＫ、ＤＩＢＫ等の飽和ケトン化合
物は、反応溶媒、塗料溶剤等として好適に用いられ、通
常アセトン、ホロン（ＰＨＯ）を原料として次のような
方法によって、工業的に製造されている。2. Description of the Related Art Saturated ketone compounds such as MIBK and DIBK are suitably used as a reaction solvent, a coating solvent and the like, and are usually produced industrially by the following method using acetone and holon (PHO) as raw materials. I have.
【０００３】[0003]
【化１】 ＭＯ、ＰＨＯの水添反応に用いる触媒としては、ニッケ
ル系触媒、ルテニウム系触媒、パラジウム系触媒、白金
系触媒等が知られている。しかし、いずれの場合も不飽
和ケトンの炭素間の二重結合への水添反応の他、カルボ
ニル基への水添反応が起こり、メチルイソブチルカルビ
ノール（ＭＩＢＣ）、ジイソブチルカルビノール（ＤＩ
ＢＣ）等のアルコール類が副生するという問題がある。Embedded image As a catalyst used for the hydrogenation reaction of MO and PHO, a nickel catalyst, a ruthenium catalyst, a palladium catalyst, a platinum catalyst, and the like are known. However, in each case, in addition to the hydrogenation reaction to the double bond between carbons of the unsaturated ketone, the hydrogenation reaction to the carbonyl group occurs, and methyl isobutyl carbinol (MIBC) and diisobutyl carbinol (DI
There is a problem that alcohols such as BC) are by-produced.
【０００４】そこで、特開昭61-85343号公開公報では、
水の共存下に、パラジウム触媒を用いてメシチルオキシ
ドを水添することにより、ＭＩＢＫの選択率を向上させ
ることが提案されている。しかし、これには、ＭＩＢＣ
の副生を抑制することについては開示されていない。Therefore, Japanese Patent Laid-Open Publication No. 61-85343 discloses that
It has been proposed to increase the selectivity of MIBK by hydrogenating mesityl oxide using a palladium catalyst in the presence of water. However, this includes MIBC
There is no disclosure of suppressing by-products.
【０００５】[0005]
【発明が解決しようとする課題】本発明者らは、ＭＩＢ
Ｃの副生を抑制しつつ、水添反応によりＭＩＢＫを製造
する方法を探索し、その結果本発明の方法に到達した。DISCLOSURE OF THE INVENTION The present inventors have found that the MIB
A method for producing MIBK by a hydrogenation reaction while suppressing the by-product of C was searched, and as a result, the method of the present invention was reached.
【０００６】[0006]
【発明の概要】即ち、本発明はアルカリの共存下に、不
飽和ケトン化合物を水添することを特徴とする飽和ケト
ン化合物の製造方法である。That is, the present invention is a process for producing a saturated ketone compound, which comprises hydrogenating an unsaturated ketone compound in the presence of an alkali.
【０００７】[0007]
【発明の具体的説明】本発明において、不飽和ケトン化
合物しては、下記一般式（Ｉ） ＲＣＯＲ’ ・・・（Ｉ） （ここで、Ｒはアルケニル基、Ｒ’はアルキル基または
アルケニル基を示す。）で示される化合物が挙げられ
る。DETAILED DESCRIPTION OF THE INVENTION In the present invention, the unsaturated ketone compound is represented by the following general formula (I): RCOR '(I) (where R is an alkenyl group, R' is an alkyl group or an alkenyl group) Is shown.).
【０００８】一般式（Ｉ）のＲ、Ｒ’において、アルキ
ル基としては、例えばメチル基、エチル基、ｎ−プロピ
ル基、ｉ−プロピル基、ｎ−ブチル基、ｉ−ブチル基、
ｔ−ブチル基、ｎ−ペンチル基、ネオペンチル基または
ｎ−ヘキシル基等の炭素数１〜６の低級アルキル基が挙
げられる。アルケニル基としては、例えば炭素数２〜６
のアルケニル基、具体的には、上記に例示したアルキル
基の任意の位置に二重結合を１つ以上有する化合物が挙
げられる。In R and R 'of the formula (I), examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group,
Examples thereof include lower alkyl groups having 1 to 6 carbon atoms, such as a t-butyl group, an n-pentyl group, a neopentyl group and an n-hexyl group. Examples of the alkenyl group include, for example, those having 2 to 6 carbon atoms.
And specifically, compounds having at least one double bond at any position of the alkyl group exemplified above.
【０００９】一般式（Ｉ）で示される不飽和ケトン化合
物の具体例としては、ＭＯ、ＰＨＯ等を挙げることがで
きる。本発明の水添方法により上記不飽和ケトン化合物
を水添することにより、対応する飽和ケトン（ＭＩＢ
Ｋ、ＤＩＢＫ等）を選択的に製造し、かつ飽和アルコー
ル（ＭＩＢＣ，ＤＩＢＣ等）の副生を抑制することがで
きる。Specific examples of the unsaturated ketone compound represented by the general formula (I) include MO, PHO and the like. By hydrogenating the above unsaturated ketone compound by the hydrogenation method of the present invention, the corresponding saturated ketone (MIB
K, DIBK, etc.) can be selectively produced, and by-products of saturated alcohols (MIBC, DIBC, etc.) can be suppressed.
【００１０】水添触媒としては、ラネーニッケルなどの
ニッケル触媒、ルテニウム触媒、パラジウム触媒、白金
触媒等を挙げることができ、好ましくはパラジウム触
媒、白金触媒を挙げることができる。パラジウム触媒と
しては、パラジウムブラック又はパラジウム−アルミ
ナ、パラジウム−カーボン等の担持パラジウム触媒が好
ましく用いられる。白金触媒としては、白金−アルミ
ナ、白金−カーボン等の担持白金触媒が好ましく用いら
れる。Examples of the hydrogenation catalyst include a nickel catalyst such as Raney nickel, a ruthenium catalyst, a palladium catalyst, a platinum catalyst and the like, and preferably a palladium catalyst and a platinum catalyst. As the palladium catalyst, a supported palladium catalyst such as palladium black or palladium-alumina or palladium-carbon is preferably used. As the platinum catalyst, a supported platinum catalyst such as platinum-alumina and platinum-carbon is preferably used.
【００１１】反応形態は特に制限されないが、バッチ式
または連続式の流動床反応方式、または固定床流通反応
方式でもよく、液相反応が好ましい。水素の供給量は、
不飽和ケトン化合物１モルに対して通常、１〜１０モ
ル、好ましくは１.１〜５モルの範囲である。水添反応
温度は通常６０℃以上、好ましくは６０〜２５０℃、さ
らに好ましくは８０〜２２０℃である。圧力は通常、大
気圧〜８ＭＰａ、好ましくは０.２〜５ＭＰａの範囲で
ある。固定床流通方式の場合、ＬＨＳＶ（液空間速度）
は特に制限されるものではないが、通常０.３〜１０ｈ
-1、好ましくは０.５〜３ｈ-1である。Although the reaction mode is not particularly limited, a batch or continuous fluidized bed reaction system or a fixed bed flow reaction system may be used, and a liquid phase reaction is preferred. The supply of hydrogen is
It is usually in the range of 1 to 10 mol, preferably 1.1 to 5 mol, per 1 mol of the unsaturated ketone compound. The hydrogenation reaction temperature is usually 60 ° C. or higher, preferably 60 to 250 ° C., and more preferably 80 to 220 ° C. The pressure is usually in the range from atmospheric pressure to 8 MPa, preferably from 0.2 to 5 MPa. LHSV (Liquid hourly space velocity)
Is not particularly limited, but is usually 0.3 to 10 h
−1 , preferably 0.5 to 3 h −1 .
【００１２】また、反応熱を効率よく除去するため、原
料を希釈して使用するのが好ましい。この場合、フレッ
シュな飽和ケトン化合物を供給して希釈するか、または
飽和ケトン化合物を主成分とする反応液を循環使用す
る。希釈剤の量は、水添反応装置に供給するメシチルオ
キシドに対し、体積比で３〜１２倍量供給するのが好ま
しい。反応液を循環使用する場合には、反応液中の飽和
アルコールの副生量が次第に増加する傾向がある。しか
し、アルカリ共存下での水添反応により、飽和アルコー
ルの副生を抑えることができる。従って反応液を循環し
ながら長時間連続運転する場合には、特にその効果が著
しい．In order to efficiently remove the heat of reaction, it is preferable to dilute the raw material before use. In this case, a fresh saturated ketone compound is supplied and diluted, or a reaction solution containing a saturated ketone compound as a main component is recycled. The amount of the diluent is preferably 3 to 12 times the volume of mesityl oxide supplied to the hydrogenation reactor. When the reaction solution is recycled, the amount of by-products of the saturated alcohol in the reaction solution tends to gradually increase. However, the hydrogenation reaction in the coexistence of an alkali can suppress the by-product of a saturated alcohol. Therefore, the effect is particularly remarkable in the case of continuous operation for a long time while circulating the reaction solution.
【００１３】アルカリ成分としては、水酸化リチウム、
水酸化カリウム、水酸化ナトリウム、炭酸ナトリウム、
炭酸水素ナトリウム等のアルカリ金属化合物、水酸化カ
ルシウム等のアルカリ土類金属化合物、アミン類、アン
モニアを例示でき、特にアルカリ金属化合物が好まし
い。アルカリの添加量は不飽和ケトンに対して通常０.
００５〜１ミリモル倍、好ましくは０.０１〜０.５ミリ
モル倍である。アルカリは原料中に溶解させて添加して
もよいが、水溶液にして系内に添加するのが好ましい。
水溶液中のアルカリ濃度は通常０．１〜１．０重量％が
好ましい。As the alkaline component, lithium hydroxide,
Potassium hydroxide, sodium hydroxide, sodium carbonate,
Examples thereof include alkali metal compounds such as sodium hydrogencarbonate, alkaline earth metal compounds such as calcium hydroxide, amines, and ammonia, and alkali metal compounds are particularly preferable. The amount of the alkali to be added is usually 0.1 to the unsaturated ketone.
The amount is from 005 to 1 mmol, preferably from 0.01 to 0.5 mmol. The alkali may be added by dissolving it in the raw material, but it is preferable to add the alkali into the system as an aqueous solution.
The alkali concentration in the aqueous solution is usually preferably from 0.1 to 1.0% by weight.
【００１４】[0014]
【発明の効果】本発明によれば、ＭＩＢＣ，ＤＩＢＣ等
の飽和アルコール類の副生を抑制しつつ、水添反応によ
り高収率でＭＩＢＫ、ＤＩＢＫ等の飽和ケトン化合物を
製造することができる。According to the present invention, a saturated ketone compound such as MIBK or DIBK can be produced at a high yield by a hydrogenation reaction while suppressing by-products of saturated alcohols such as MIBC and DIBC.
【００１５】[0015]
【実施例】以下実施例に基づいて本発明を説明するが、
本発明はこれらの実施例に限られるものではない。EXAMPLES The present invention will be described below with reference to examples.
The present invention is not limited to these examples.
【００１６】実施例１ 図１の装置を用い、粗メシチルオキシドを水添しＭＩＢ
Ｋの製造を行った。水添反応器（直径２５ｍｍφ×長さ
１００７ｍｍ）にパラジウム−カーボン触媒（ＮＥケム
キャット社製：破砕状，粒径４〜８メッシュ，パラジウ
ム担持量０.５％）１００ｍｌを仕込み、メシチルオキ
シド溶液（メシチルオキシド濃度９０.４％）を１００
ｍｌ／ｈならびに反応熱除去のためＭＩＢＫ（純度９
９.８４％）を８００ｍｌ／ｈ供給しながら、反応圧力
０.９８ＭＰａ、メシチルオキシドに対するＨ2のモル比
４、反応温度（触媒層中で最も高い温度）１２５℃の反
応系へ０.５％ＮａＯＨaq.を１ｍｌ／ｈ供給したとこ
ろ、メシチルオキシド転化率９９.９６モル％で，ＭＩ
ＢＫ選択率９９.１９モル％、ＭＩＢＣの選択率は０.６
０モル％の反応成績が得られた。なお、この場合の反応
液中の水分濃度は０.５６％であった。Example 1 Using the apparatus shown in FIG. 1, crude mesityl oxide was hydrogenated to obtain MIB.
K was manufactured. A hydrogenation reactor (diameter 25 mmφ × length 1007 mm) was charged with 100 ml of a palladium-carbon catalyst (manufactured by NE Chemcat, crushed, particle size 4 to 8 mesh, palladium carrying amount 0.5%), and a mesityl oxide solution ( Mesityl oxide concentration of 90.4%)
ml / h and MIBK (purity 9
(9.84%) at a reaction pressure of 0.98 MPa, a molar ratio of H 2 to mesityl oxide of 4, and a reaction temperature of 0.5 ° C. (the highest temperature in the catalyst layer) of 125 ° C. while supplying 800 ml / h. % NaOHaq. Was supplied at a rate of 1 ml / h, the conversion of mesityl oxide was 99.96 mol%,
BK selectivity 99.19 mol%, MIBC selectivity 0.6
A reaction result of 0 mol% was obtained. In this case, the water concentration in the reaction solution was 0.56%.
【００１７】 （分析方法） 水分含量 ：カールフィッシャー水分計 ＭＯ，ＭＩＢＫ、ＭＩＢＣ ：ガスクロマトグラフィー(Analysis method) Moisture content: Karl Fischer moisture meter MO, MIBK, MIBC: Gas chromatography
【００１８】実施例２ ０.２％の ＮａＯＨａｑ.を供給した以外は実施例１と
同じ方法でメシチルオキシドの水添を行ったところ、メ
シチルオキシド転化率９９.９８モル％で、ＭＩＢＫ選
択率９８.８８モル％、ＭＩＢＣの選択率は０．８２モ
ル％の反応成績が得られた。なお、この場合の反応液中
の水分濃度は０.５８％であった。Example 2 The hydrogenation of mesityl oxide was carried out in the same manner as in Example 1 except that 0.2% of NaOHaq. Was supplied. The reaction yield was 98.88 mol% and the selectivity of MIBC was 0.82 mol%. In this case, the water concentration in the reaction solution was 0.58%.
【００１９】比較例１ ＮａＯＨaq.を供給しない以外は実施例１と同じ方法で
メシチルオキサイドの水添反応を行ったところ、メシチ
ルオキシド転化率９９.９６モル％で、ＭＩＢＫ選択率
９８.５０モル％、ＭＩＢＣの選択率は１.５０モル％の
反応成績であった。なお、この場合の反応液中の水分濃
度は０.４５％であった。Comparative Example 1 A hydrogenation reaction of mesityl oxide was carried out in the same manner as in Example 1 except that NaOHaq. Was not supplied. The mol% and the selectivity of MIBC were 1.50 mol%. In this case, the water concentration in the reaction solution was 0.45%.
【００２０】[0020]
【図１】は実施例１で用いた装置の概要である。FIG. 1 is an outline of an apparatus used in Example 1.
フロントページの続き (72)発明者 平井 茂正 山口県玖珂郡和木町和木六丁目１番２号三 井化学株式会社内 Ｆターム(参考） 4H006 AA02 AC11 AD11 BA02 BA06 BA21 BA23 BA25 BA26 BA29 BA32 BA61 BR10 Continued on the front page (72) Inventor Shigemasa Hirai 6-1-2, Waki, Waki-machi, Kuga-gun, Yamaguchi Prefecture F-term (reference) in Mitsui Chemicals, Inc. 4H006 AA02 AC11 AD11 BA02 BA06 BA21 BA23 BA25 BA26 BA29 BA32 BA61 BR10
Claims (2)
水添することを特徴とする飽和ケトン化合物の製造方
法。1. A process for producing a saturated ketone compound, comprising hydrogenating an unsaturated ketone compound in the presence of an alkali.
アルケニル基を示す。）で示される化合物であることを
特徴とする請求項１記載の方法。2. An unsaturated ketone compound represented by the following general formula (I): RCOR '(I) wherein R represents an alkenyl group and R' represents an alkyl group or an alkenyl group. The method of claim 1, wherein
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02108599A JP3939042B2 (en) | 1999-01-29 | 1999-01-29 | Method for producing saturated ketone compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02108599A JP3939042B2 (en) | 1999-01-29 | 1999-01-29 | Method for producing saturated ketone compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000219649A true JP2000219649A (en) | 2000-08-08 |
| JP3939042B2 JP3939042B2 (en) | 2007-06-27 |
Family
ID=12045053
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP02108599A Expired - Lifetime JP3939042B2 (en) | 1999-01-29 | 1999-01-29 | Method for producing saturated ketone compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3939042B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101717328A (en) * | 2009-09-14 | 2010-06-02 | 广西万山香料有限责任公司 | New method for synthesizing raspberry ketone by using natural equivalent anisic aldehyde |
| CN105732305A (en) * | 2016-03-25 | 2016-07-06 | 中南大学 | Preparation method for synthesis of methyl isobutyl ketone and methyl isobutyl alcohol |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103755537B (en) * | 2014-01-14 | 2015-11-04 | 浙江新化化工股份有限公司 | The co-production of a kind of hexone and diisobutyl ketone |
-
1999
- 1999-01-29 JP JP02108599A patent/JP3939042B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101717328A (en) * | 2009-09-14 | 2010-06-02 | 广西万山香料有限责任公司 | New method for synthesizing raspberry ketone by using natural equivalent anisic aldehyde |
| CN105732305A (en) * | 2016-03-25 | 2016-07-06 | 中南大学 | Preparation method for synthesis of methyl isobutyl ketone and methyl isobutyl alcohol |
| CN105732305B (en) * | 2016-03-25 | 2018-05-25 | 中南大学 | A kind of preparation method of synthesizing methyl isobutyl ketone and methyl isobutyl alcohol |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3939042B2 (en) | 2007-06-27 |
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