JPS61207354A - Production of ketone - Google Patents
Production of ketoneInfo
- Publication number
- JPS61207354A JPS61207354A JP60047979A JP4797985A JPS61207354A JP S61207354 A JPS61207354 A JP S61207354A JP 60047979 A JP60047979 A JP 60047979A JP 4797985 A JP4797985 A JP 4797985A JP S61207354 A JPS61207354 A JP S61207354A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- ketone
- boiling point
- phase reaction
- reaction
- 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
Classifications
-
- 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
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、ケトン類の改良された製造方法に関するもの
である。更に詳しくは、高沸点有機溶媒中に懸濁させた
酸化ジルコニウムを触媒に用いて、カルボン酸より相当
するケトンを液相反応で製造する方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to an improved method for producing ketones. More specifically, the present invention relates to a method for producing a corresponding ketone from a carboxylic acid in a liquid phase reaction using zirconium oxide suspended in a high-boiling organic solvent as a catalyst.
ケトン類はゴム、プラスチックス、塗料等の汎用溶剤、
農薬等の中間体として有用なものである。Ketones are general-purpose solvents for rubber, plastics, paints, etc.
It is useful as an intermediate for agricultural chemicals, etc.
従来、カルボン酸から相当するケトンを製造する方法で
は、気相接触反応で、触媒として酸化カルシウム、アル
ミナ、酸化ジルコニウム等を用いる方法が提案されてい
る。しかしながら、これらの方法は気相接触反応による
為、高温が必要であり、エネルギー消費が多（、また装
置も汎用性に乏しく、少量多品種製造が多くなっている
現在の化学工業界では必らずしも工業的に有利な方法で
はない。Conventionally, as a method for producing a corresponding ketone from a carboxylic acid, a method using calcium oxide, alumina, zirconium oxide, etc. as a catalyst in a gas phase catalytic reaction has been proposed. However, since these methods rely on gas-phase catalytic reactions, they require high temperatures and consume a lot of energy (and the equipment is not very versatile, making them indispensable in the current chemical industry where there is a lot of small-lot, high-mix production. Sushi is also not an industrially advantageous method.
本発明者らは、液相反応によるカルボン酸類からのケト
ン類の製造において鋭意検討し、工業的に優れた製造方
法を見い出した。The present inventors have conducted intensive studies on the production of ketones from carboxylic acids by liquid phase reaction, and have discovered an industrially excellent production method.
即ち、本発明は触媒を懸濁させた高沸点有機溶媒中で、
カルボン酸類を液相反応させて、ケトン類を合成するに
際し、触媒として酸化ジルコニウムを用いることを特徴
とするケトン類の製造法である。That is, in the present invention, in a high boiling point organic solvent in which a catalyst is suspended,
This method for producing ketones is characterized by using zirconium oxide as a catalyst when synthesizing ketones by subjecting carboxylic acids to a liquid phase reaction.
本発明において用いる酸化ジルコニウム触媒は通常の方
法によって調製することができる。The zirconium oxide catalyst used in the present invention can be prepared by a conventional method.
例えば、市販の酸化ジルコニウムの粉末を直接か、水酸
化ジルコニウムを焼成して得たものを用いる。後者の場
合、焼感温度は４００〜７００℃が適当であり、焼成温
度が高いときは最適反応温度が高温側にづれ、工業的に
は不利となる。For example, commercially available zirconium oxide powder may be used directly, or zirconium hydroxide obtained by firing may be used. In the latter case, the appropriate firing temperature is 400 to 700°C, and when the firing temperature is high, the optimum reaction temperature shifts to the high temperature side, which is industrially disadvantageous.
高沸点有機溶剤としては、沸点は生成ケトンより高いも
のであり、好ましくは２５０℃以上の高沸点炭化水素が
よい。例えば、流動パラフィン、ジエチルジフェニル（
商品名：サームエス７００）（新日本製鉄化学社品。以
下同じ。）トリエチルジフェニル（商品名：サームエス
６００ ）、水素化トリフェニル（商品名：サームエス
９００ ）等である。The high boiling point organic solvent is one having a boiling point higher than that of the produced ketone, preferably a high boiling point hydrocarbon having a boiling point of 250° C. or higher. For example, liquid paraffin, diethyl diphenyl (
These are triethyl diphenyl (trade name: THERM-S 600), hydrogenated triphenyl (trade name: THERM-S 900), etc.
本発明において用いるカルボン酸類としては、酢酸、プ
ロピオン酸、１３ｏ−酪酸、ルー酪酸等の炭素数が２〜
５の一塩基酸、さらにはアジピン酸等の炭素数が５〜１
０の二塩基酸が適当である。Examples of carboxylic acids used in the present invention include acetic acid, propionic acid, 13o-butyric acid, and lubutyric acid having 2 to 2 carbon atoms.
5 monobasic acid, and furthermore, adipic acid with 5 to 1 carbon atoms.
0 dibasic acids are suitable.
反応原料としては、これらの一種を単独、あるいは二種
以上の混合物で使用することができる。As the reaction raw material, one of these may be used alone or a mixture of two or more may be used.
本発明を実施する場合、通常反応は高沸点有機溶媒中に
該触媒を懸濁し、反応速度に応じた速度で原料、カルボ
ン酸を仕込み、生成したケトンを反応系外へ溜出させる
ことからなる。When carrying out the present invention, the reaction usually consists of suspending the catalyst in a high-boiling organic solvent, charging the raw material and carboxylic acid at a rate corresponding to the reaction rate, and distilling the produced ketone out of the reaction system. .
また゛、次のような操作条件が採用される。反応温度は
２５０〜９５０℃が好まし℃・。反応温度が高いと有機
溶媒が生成ケトンと共に溜出し易くなる。また、反応温
度が低いと、充分な変化率が得られない。有機溶媒中の
触媒濃度は１〜２０％でよい。原料カルボン酸の仕込み
速度は反応温度、触媒濃度等によって異なるが、使用触
媒重量の０．０５〜１．０倍量／１時間当りにするのが
適当である。In addition, the following operating conditions are adopted. The reaction temperature is preferably 250 to 950°C. When the reaction temperature is high, the organic solvent tends to distill out together with the produced ketone. Furthermore, if the reaction temperature is low, a sufficient rate of change cannot be obtained. The concentration of catalyst in the organic solvent may be between 1 and 20%. The charging rate of the raw material carboxylic acid varies depending on the reaction temperature, catalyst concentration, etc., but is suitably 0.05 to 1.0 times the weight of the catalyst used/per hour.
得られた反応生成液は必要に応じて周知の方法、例えば
、（減圧）蒸溜等によって精製され、目的物を得ること
ができる。The obtained reaction product liquid can be purified, if necessary, by a well-known method such as (reduced pressure) distillation to obtain the desired product.
以下、実施例において更に具体的に説明する。 A more specific explanation will be given below in Examples.
なお、成績は反応生成液のガスクロマトグラフィにより
分析して求めた。The results were obtained by analyzing the reaction product liquid by gas chromatography.
実施例１゜
市販の水酸化ジルコニウム（ＺｒＯｚ として７０％含
有する。）を５００℃で３時間焼成して触媒を得た。Example 1 Commercially available zirconium hydroxide (containing 70% as ZrOz) was calcined at 500° C. for 3 hours to obtain a catalyst.
攪拌機を備えた５００ｍ１のガラス反応器に、流動パラ
フィン３００ｇと上記で得た触媒４５９を仕込み、３３
０℃に加熱する。次いで攪拌下、反応温度でプロピオン
酸を毎時ＩＱｍｌの速度で連続的に仕込み、反応器の上
部より生成したジエチルケトンを連続的に系外へ溜出さ
せた。A 500 ml glass reactor equipped with a stirrer was charged with 300 g of liquid paraffin and the catalyst 459 obtained above.
Heat to 0°C. Next, propionic acid was continuously charged at a rate of IQml/hour at the reaction temperature under stirring, and diethyl ketone produced from the upper part of the reactor was continuously distilled out of the system.
反応時間は９６Ｈｒであった。The reaction time was 96 hours.
結果、プロピオン酸の変化率９９．２％、ジエチルケト
ンの収率９６，０％を得た。As a result, a conversion rate of propionic acid of 99.2% and a yield of diethyl ketone of 96.0% were obtained.
実施例λ
実施例１と同一の触媒を用い、反応温度及び原料の仕込
み速度を変更した以外は実施例１と同一の方法で反応し
、下記の結果を得た。Example λ The same catalyst as in Example 1 was used, and the reaction was carried out in the same manner as in Example 1 except that the reaction temperature and raw material charging rate were changed, and the following results were obtained.
実施例３． ・
市販の水酸化ジルコニウム（Ｚ ｒ ０２として７０％
含有する。）を４００℃で焼成した触媒を用い、反応温
度を変更した以外は実施例１と同一の方法で反応し、下
記の結果を得た。Example 3. - Commercially available zirconium hydroxide (70% as Z r 02)
contains. ) was calcined at 400° C., and the reaction was carried out in the same manner as in Example 1 except that the reaction temperature was changed, and the following results were obtained.
比較例
触媒をｒ−アルミナに変更した以外は、実施例１と同一
の方法で反応した。Comparative Example The reaction was carried out in the same manner as in Example 1, except that r-alumina was used as the catalyst.
結果、プロピオン酸の変化率２２．６％、ジエチルケト
ンの収率１３．１％を得た。As a result, a conversion rate of propionic acid of 22.6% and a yield of diethyl ketone of 13.1% were obtained.
実施例４゜
実施例１と同一の反応器を利用して、実施例１で用℃・
た触媒２５ｇ、流動パラフィン３００ｇ及びアジピン酸
５０ｇを混合し、２８０℃に加熱した。反応温度で２Ｈ
ｒ経過後、反応器の上部より生成液２９．７ ｇを得た
。。Example 4 Using the same reactor as in Example 1,
25 g of the prepared catalyst, 300 g of liquid paraffin, and 50 g of adipic acid were mixed and heated to 280°C. 2H at reaction temperature
After 3 hours, 29.7 g of product liquid was obtained from the upper part of the reactor. .
結果、シクロペンタノンの純１ｉ８０．３％、シクロペ
ンタノンの収率８２．９％であった。As a result, the purity of cyclopentanone was 80.3%, and the yield of cyclopentanone was 82.9%.
Claims (1)
液相反応させて、ケトン類を合成するに際し、触媒とし
て酸化ジルコニウムを用いることを特徴とするケトン類
の製造法。A method for producing ketones, which comprises using zirconium oxide as a catalyst in synthesizing ketones by subjecting carboxylic acids to a liquid phase reaction in a high-boiling organic solvent in which a catalyst is suspended.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60047979A JPS61207354A (en) | 1985-03-11 | 1985-03-11 | Production of ketone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60047979A JPS61207354A (en) | 1985-03-11 | 1985-03-11 | Production of ketone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61207354A true JPS61207354A (en) | 1986-09-13 |
| JPH0516419B2 JPH0516419B2 (en) | 1993-03-04 |
Family
ID=12790428
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60047979A Granted JPS61207354A (en) | 1985-03-11 | 1985-03-11 | Production of ketone |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61207354A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4929761A (en) * | 1986-12-22 | 1990-05-29 | Amoco Corporation | Preparation of substituted benzophenones |
| WO2001028967A1 (en) * | 1999-10-20 | 2001-04-26 | Rhodia Chimie | Method for preparing ketones by pyrogenic reaction of aldehydes, alcohols, acids or esters |
| JP2022006517A (en) * | 2020-06-24 | 2022-01-13 | 正晴 銅谷 | Production method of 3-methylcycloalkenones |
-
1985
- 1985-03-11 JP JP60047979A patent/JPS61207354A/en active Granted
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4929761A (en) * | 1986-12-22 | 1990-05-29 | Amoco Corporation | Preparation of substituted benzophenones |
| WO2001028967A1 (en) * | 1999-10-20 | 2001-04-26 | Rhodia Chimie | Method for preparing ketones by pyrogenic reaction of aldehydes, alcohols, acids or esters |
| FR2800066A1 (en) * | 1999-10-20 | 2001-04-27 | Rhodia Chimie Sa | Process for the preparation of ketones by a pyrogenic reaction of aldehydes, alcohols, acids or esters in liquid phase and in the presence of a catalyst |
| US6639112B1 (en) | 1999-10-20 | 2003-10-28 | Rhodia Chimie | Method for preparing ketones by pyrogenic reaction of aldehydes, alcohols, acids or esters |
| JP2022006517A (en) * | 2020-06-24 | 2022-01-13 | 正晴 銅谷 | Production method of 3-methylcycloalkenones |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0516419B2 (en) | 1993-03-04 |
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